DE112018001795T5 - ALL-SOLID-STATE BATTERY - Google Patents

Abstract

The purpose of the present invention is to provide a high discharge capacity in an all solid state battery in which lithium vanadium phosphate is used in a positive electrode active material layer and a negative electrode active material layer. The present invention provides an all-solid-state battery, wherein a positive electrode active material layer and a negative electrode active material layer contain lithium vanadium phosphate, which contains a Li and V-containing polyphosphate compound and 1.50 <Li / V≤2, 30 is satisfied, the percentage of bivalent V contained in the V being 5-80%. A high discharge capacity can thus be provided.

Description

The present invention relates to an all-solid-state battery with the advantages of high discharge capacity, high safety and low costs.

TECHNICAL BACKGROUND

With the development of portable machines such as PCs and portable telephones, the demand for batteries as an energy source has increased significantly in recent years. Batteries for such purposes have used liquid electrolyte (electrolyte liquid) such as organic solvents as a medium for moving ions in the past. When using batteries with such an electrolytic liquid, problems such as the leakage of electrolytic liquid can occur.

To solve this problem, all-solid-state batteries are currently being developed which use solid electrolyte instead of liquid electrolyte and which are composed of solids with regard to the other elements. Because the electrolyte of the all solid state batteries is solid, all solid state batteries have no concerns about fluid leakage and fluid depletion. Furthermore, there are hardly any problems such as the deterioration in battery performance caused by corrosion. Here, all-solid-state batteries as accumulators that can easily achieve a high charge / discharge capacity and energy density are actively researched in various aspects.

So far, there has been a problem with a smaller discharge capacity in the case of all-solid-state batteries in which solid electrolyte is used as the electrolyte, compared to batteries in which liquid electrolyte is used. Even though the use of Li ₃ V ₂ (PO ₄ ) ₃ made of a polyphosphate active electrode material with multiple redox potentials (3.8 V, 1.8 V) for positive electrodes and negative electrodes for the production of batteries with a symmetrical electrode has been disclosed to the To improve properties of a charge / discharge cycle, the improvement in discharge capacity (in Patent Document 1) has not been disclosed. In the event that stoichiometric Li ₃ V ₂ (PO ₄ ) _{3 is also used} as the active material of a sintered body for positive electrodes or negative electrodes, the constituents of the crystal grain boundaries formed during sintering may become uneven and lithium ion conductivity may be hindered. Therefore, there is a technical problem in that a high discharge capacity cannot be achieved.

Therefore, there is still a need for improvement in terms of the discharge capacity for all the all-solid-state batteries disclosed in Patent Document 1.

Patent documents

Patent document 1: JP 2007-258165

PRESENTATION

The present invention has been made against the background of the problems in the prior art, and its object is to provide an all-solid-state battery with a high discharge capacity.

In order to solve the above technical problems, the inventors conducted a comprehensive study. The results show that the positive electrode active material layer and the negative electrode active material layer contain lithium vanadium phosphate, that the lithium vanadium phosphate contains a polyphosphate compound containing Li and V, and that the ratio of Li to V contained and the proportion of bivalent V contained in V are due to the capacitance, so that the present invention is achieved.

In other words, the present invention provides an all-solid-state battery as follows.

The all-solid-state battery provided by the invention is an all-solid-state battery that is provided with a solid electrolyte layer between a pair of electrodes, characterized in that a positive electrode active material layer and a negative electrode active material layer, the pair of electrodes form, contain lithium vanadium phosphate, the lithium vanadium phosphate contains a polyphosphate compound which contains Li and V and fulfills 1.50 <Li / V≤2.30, and the proportion of bivalent V contained in V 5% Is ~ 80%.

Using the positive electrode active material layer and the negative electrode active material layer according to the composition, the lithium ions in the lithium vanadium phosphate can be stably present in crystal lattices, and the excessive diffusion of Li during sintering can be controlled so as to form a uniform grain boundary, and the reduction in lithium ion conductivity between the grains can be prevented. As a result, a large number of lithium ions can be exported and introduced, and therefore a high capacity can be achieved.

The all-solid-state battery provided by the present invention is characterized in that the solid-state electrolyte layer contains lithium-aluminum-titanium phosphate.

According to the composition, movement of lithium ions in the positive electrode active material layer and the negative electrode active material layer becomes easier. At the same time, movement of lithium ions in the solid electrolyte layer between the positive electrode active material layer and the negative electrode active material layer becomes easier. Therefore, an even higher capacity can be achieved.

The all-solid-state battery provided by the present invention is characterized in that the value of Li / V of the lithium vanadium phosphate contained in the positive electrode active material layer is larger than the value of Li / V of the lithium -Vanadium phosphate contained in the negative electrode active material layer.

According to the composition, the positive electrode active material layer contains more Li than the negative electrode active material layer, therefore more Li moves from the positive electrode active material layer to the negative electrode active material layer, and more Li can be taken up in the negative electrode active material layer. Therefore, an even higher capacity can be achieved.

The all-solid state battery provided by the present invention is characterized in that the positive electrode active material layer satisfies 1.60≤Li / V≤2.30 and the proportion of bivalent V in V is 10% ~ 80%, and that negative electrode active material layer satisfies 1.50 <Li / V≤2.10, and the proportion of bivalent V in V is 5% ~ 57%.

By using the positive electrode active material layer and the negative electrode active material layer having the composition, the positive electrode active material layer contains more Li than the negative electrode active material layer, therefore more Li moves from the positive electrode active material layer to the negative electrode active material layer and more Li can be taken up in the negative electrode active material layer. Furthermore, since the positive electrode active material layer contains more divalent V than the negative electrode active material layer, lithium ions in the crystal lattices can be made more stable. By forming uniform grain boundaries, the reduction in lithium ion conductivity between the grains can be prevented, and thus an even higher capacity can be achieved.

The all-solid-state battery provided by the present invention is characterized in that the solid electrolyte contains Li _f Al _g Ti _h P _i O _j (where f, g, h, i and j are each values that are 0.5 ≤f≤3.0; 0.0 <g≤1.0;1.0≤h≤2.0;2.8≤i≤3.2; and 9.25 <j≤15.0).

According to the composition, using Li _f Al _g Ti _h P _i O _j (where f, g, h, i and j are values that are 0.5≤f≤3.0; 0.0 <g≤1, respectively , 0; 1.0≤h≤2.0; 2.8≤i≤3.2; and 9.25 <j≤15.0) with high lithium ion conductivity as lithium-aluminum-titanium-phosphate of the solid electrolyte layer higher capacity can be achieved.

The all-solid state battery provided by the present invention is characterized in that the relative density of the pair of electrode layers and the solid electrolyte layer interposed between the pair of electrode layers is 80% or more.

According to the present invention, the all-solid state battery with high discharge capacity can be provided.

list of figures

• 1 FIG. 12 is a diagram illustrating an all-solid state battery according to the embodiment.

DETAILED DESCRIPTION OF EMBODIMENTS

The preferred examples of the present invention are described in detail below with reference to the drawings. It is noted that the same or equivalent parts in the drawings are given the same reference numerals and the description of repetitive parts is omitted. Furthermore, the size scale of the drawings is not limited to the scale shown.

All-solid-state battery

1 is a diagram showing the structural design of an all solid state battery 1 according to the present embodiment. As in 1 a positive electrode layer is shown 2 and a negative electrode layer 3 the all-solid-state battery 1 according to the embodiment with a solid electrolyte layer 4 laminated between them, the positive electrode layer 2 consists of a packing layer 5 , a positive electrode current collector layer 6 , and a positive electrode active material layer 7 ; and the negative electrode layer 3 consists of a negative electrode active material layer 7 and a negative electrode current collector layer 8th and a packing layer 5 ,

The all-solid-state battery according to the present embodiment is an all-solid-state battery provided with a solid electrolyte layer between a pair of electrode layers, a positive electrode active material layer and a negative electrode active material layer forming the pair of electrode layers, Contain lithium vanadium phosphate, the lithium vanadium phosphate contains a Li and V-containing polyphosphate compound and fulfills 1.50 <Li / V≤2.30, and the proportion of bivalent V contained in the V is preferred Is 5% ~ 80%.

According to the composition, when using the positive electrode active material layer or the negative electrode active material layer, the lithium ions in the lithium vanadium phosphate can be stably present in crystal lattices, and the excessive diffusion of Li during sintering can be controlled so that a uniform grain boundary can be formed, and that Reduction of lithium ion migration between the grains can be prevented. As a result, a large number of lithium ions can be introduced and exported, which is why a high capacity can be achieved.

Note that for the lithium vanadium phosphate in the present embodiment, the material is quantitatively analyzed using high frequency emission spectroscopy using Inductively Coupled Plasma (ICP), and Li / V is calculated. Furthermore, the valence of V in the lithium vanadium phosphate can be obtained from chemical shift by X-ray photoelectron spectroscopy (XPS).

Furthermore, in the all-solid-state battery according to the present embodiment, the solid electrolyte layer preferably contains lithium aluminum titanium phosphate.

According to the composition, if a solid electrolyte containing lithium aluminum titanium phosphate is used in the solid electrolyte layer, even the movement of lithium ions between the positive electrode layers and the negative electrode layers becomes easier for the purpose of high ion conductivity of the solid electrolyte, and therefore achieves a higher capacity can be. Furthermore, the solid electrolyte containing the active material lithium vanadium phosphate and lithium aluminum titanium phosphate according to the present embodiment is a homogeneous polyphosphate ceramic, and therefore it is not easy to form uneven grain boundaries at these interfaces, which the Can prevent movement of lithium ions, and thus the charge / discharge capacity can be improved.

Further, in the all-solid state battery according to the present embodiment, the value of Li / V in the positive electrode active material layer is larger than the value of Li / V in the negative electrode active material layer.

According to the composition, the positive electrode active material layer contains more Li than the negative electrode active material layer, thus more Li moves from the positive electrode active material layer to the negative electrode active material layer, and more Li can be taken up in the negative electrode active material layer. Therefore, an even higher capacity can be achieved.

In the all-solid-state battery according to the present embodiment, it is further preferable that Li / V of the lithium vanadium phosphate in the positive electrode active material layer satisfies 1.6≤Li / V≤2.3 and the proportion of bivalent V contained in V is 10% ~ 80%, and Li / V of lithium vanadium phosphate in the negative electrode active material layer satisfies 1.5 <Li / V≤2, 1 and the proportion of bivalent V contained in V is included is 5% ~ 57%.

According to the composition, using the positive active material layer and the negative electrode active material layer, the positive electrode active material layer contains more Li than the negative electrode active material layer and thus more Li moves from the positive electrode active material layer to the negative electrode active material layer and more Li can be taken up in the negative electrode active material layer. Furthermore, by causing the positive electrode active material layer to contain more divalent V than the negative electrode active material layer, lithium ions can be made to be more stable in the crystal lattices. By forming uniform grain boundaries, the decrease in lithium ion conductivity between grains can be prevented, and thus an even higher capacity can be achieved.

Furthermore, although the reason for this is not clear, it is believed that by respectively exchanging Li / V of lithium vanadium phosphate and the proportion of bivalent V in V in the positive electrode active material layer and the negative electrode active material layer, the crystal grain boundaries that exist during it Sintering are formed, a composition structure which can be used in a simple manner for the functioning of the positive electrode, and a composition structure which is suitable for the functioning of the negative electrode.

In the all-solid-state battery provided by the invention, Li _f Al _g Ti _h P _i O _j with high lithium ion conductivity is preferably used as the lithium aluminum titanium phosphate (where f, g, h, i and j are values, that meet 0.5≤f≤3.0, 0.0 <g≤1.0, 1.0≤h≤2.0, 2.8≤i≤3.20 and 9.25 <j≤15.0) ,

According to the composition, by using Li _f Al _g Ti _h P _i O _j with high lithium ion conductivity as lithium aluminum titanium phosphate (where f, g, h, i and j are values that are 0.5≤f≤3, 0, 0.0 <g≤1.0, 1.0≤h≤2.0, 2.8≤i≤3.2 and 9.25 <j≤15.0), higher charging / discharging properties be achieved.

Process for producing the ceramic material

The lithium vanadium phosphate material of the present embodiment can be obtained by heat-treating the raw material mixture, which is a mixture of a Li compound, a V compound and a phosphate compound or a Li phosphate compound. Furthermore, the lithium aluminum titanium phosphate material can be obtained by heat treating the material mixture, which is a mixture of a Li compound, an Al compound, a Ti compound, a phosphate compound or a Ti phosphate compound. Connection.

As Li compound, LiOH or its hydrate, Li ₂ CO ₃ , LiNO ₃ , CH ₃ COOLi and the like may be mentioned. V ₂ O ₃ , V ₂ O ₅ and the like may be mentioned as the V-connection. H ₃ PO ₄ , NH ₄ H ₂ PO ₄ and (NH ₄ ) ₂ HPO ₄ may be mentioned as the phosphate compound. Furthermore, LiPO ₃ , Li ₄ P ₂ O ₇ , Li ₅ P ₃ O ₁₀ , Li ₆ P ₄ O ₁₄ and the like may be mentioned as Li-phosphate compound.

Furthermore, Al ₂ O ₃ , Al (OH) ₃ , Al ₂ (SO ₄ ) ₃ and the like may be mentioned as the Al compound. As the Ti compound, there may be mentioned TiO ₂ , Ti ₂ O ₃ , TiCl ₄ , Ti (OR) ₄ and the like. As a Ti-phosphate compound, TiP ₂ O ₇ , Ti ₃ P ₄ O ₁₆ and the like may be mentioned.

An example of producing the lithium vanadium phosphate according to the present embodiment will be described. The process for producing the oxide again involves performing the following processes, i.e. (a) process for mixing raw material, then (b) heat treatment process, and finally (c), a crushing process. These processes are described sequentially below.

Process of mixing raw material

In the process of mixing raw material in lithium vanadium phosphate, starting materials are weighed out and mixed in such a way that the ratio of Li to V is 1.5 <Li / V≤2.30. As the raw materials, carbonate or sulfate, nitrate, oxalate, chloride, hydroxide, oxide, phosphate and the like of various elements can be used. It is preferred that the raw materials or Oxides obtained as lithium phosphate, which do not generate unnecessary gases during the heat treatment, and carbonate, which generates carbon dioxide, or hydroxide, which generates water vapor by thermal decomposition, are particularly preferred. Regarding the mixing process, dry mixing and crushing without solvent or wet mixing and crushing in solvent can be used. In view of improved mixing performance, wet mixing and grinding in solvent are preferred. In a mixing process, for example, a planetary mixer, an attritor or a ball mill can be used. Substances in which Li is not soluble are preferred as solvents. For example, organic solvents such as ethanol are preferred. The mixing time depends on the amount to be mixed. For example, it can be set to 1h to 32h. Furthermore, in the case of the lithium aluminum titanium phosphate, the starting materials are each weighed out in order to obtain the desired composition and then mixed using one of the methods mentioned.

calcination

In the calcining process, the powder mixture obtained in the mixing process is calcined in lithium vanadium phosphate. At this time, the calcining temperature is preferably higher than the temperature that causes the change in the state of the raw materials (e.g., a phase change). For example, if Li ₂ CO _{3 is} used as one of the starting materials, the temperature is preferably the temperature at which the carbonate decomposes in order to obtain the desired lithium-vanadium-phosphate phase or the aforementioned ones. In addition, the calcination temperature is preferably 600 ° C ~ 1000 ° C. Furthermore, to control the amount of bivalent V in V in lithium vanadium phosphate, the air envelope during the calcination is preferably an inert gas envelope or a reducing gas envelope. In addition, even with the lithium aluminum titanium phosphate, the powder mixture obtained in the mixing process is also calcined. Specifically, the calcination temperature is preferably 800 ° C to 1000 ° C. In addition, the air envelope during the calcination is preferably an air envelope in which titanium is not reduced, in particular an atmospheric gas envelope.

crushing process

During comminution, it becomes a process in which the materials clump together by reaction during the calcining process to be processed into powder with a suitable particle size and distribution. The grinding process can be dry grinding without solvent or wet grinding in solvent. A planetary mixer, an attritor, a ball mill or the like can be used in the comminution process, for example. Organic solvents such as ethanol are preferred as solvents in order to enable the crushing of the lithium vanadium phosphate. The shredding time depends on the amount to be shredded. For example, it can be set from 0.5 h to 32 h.

According to the manufacturing method described in detail above, the powder mixture of the starting materials is calcined at a relatively low temperature, so that the deviation of the composition can be controlled precisely. Furthermore, the method for producing lithium vanadium phosphate in the present invention is not limited to this, and other production methods can be used.

In the all-solid-state battery according to the present embodiment, a positive electrode layer 2 and a negative electrode layer 3 with a solid electrolyte layer arranged between them 4 laminated. The positive electrode layer 2 consists of a packing layer 5 , a positive electrode current collector layer 6 and a positive electrode active material layer 7 , The negative electrode layer 3 consists of a negative electrode active material 8th , a negative electrode current collector layer 9 and a packing layer 5 , The positive electrode current collector layer 6 and the negative electrode current collector layer 9 can contain known collectors that are used in lithium batteries and can be manufactured using conventional methods.

current collector

Materials with high conductivity, such as silver, palladium, gold, platinum, aluminum, copper, nickel or the like, are preferably used in the current collector layer of the all-solid-state battery according to the present invention. In particular, it is difficult to react copper with lithium aluminum titanium phosphate, it has an effect of reducing the internal resistance of the all-solid-state battery, and is therefore preferred. The materials that form the current collector layers can be the same materials or different materials in the positive electrode layer and the negative electrode layer.

Furthermore, the positive electrode current collector layer and the negative electrode current collector layer of the all-solid-state battery in the present embodiment preferably include a positive electrode active material and a negative electrode active material.

By having the positive electrode current collector layer and the negative electrode current collector layer containing the positive electrode active material and the negative electrode active material, respectively, the adhesion between the positive electrode current collector layer and the positive electrode active material layer and the adhesion between the negative electrode current collector layer and the negative electrode active material layer are improved, and thus they are preferred ,

Process for manufacturing the all-solid-state battery

The all-solid-state battery according to the present embodiment is manufactured by using the following method, i.e. Processing of the materials of the positive electrode current collector layer, the positive electrode active material layer, the solid electrolyte layer, the negative electrode active material layer and the negative electrode current collector layer into paste, carrying out coating and drying to obtain green foils, laminating the green foils and sintering the produced laminated body.

The method for processing the paste is not specifically limited. For example, the powder of the materials can be mixed in the carrier liquid to obtain the paste. The carrier liquid is the general term for media in the liquid phase. The carrier liquid contains solvents and binders. The paste for the positive electrode current collector layer, the paste for the positive electrode active material layer, the paste for the solid electrolyte layer, the paste for the negative electrode active material layer and the paste for the negative electrode current collector layer are prepared using the method described above.

The paste produced is applied to substrates such as PET in the desired order. After drying as required, the substrates are stripped off to obtain green foils. The paste coating method is not specifically limited. Well-known methods such as screen printing, coating, transfer printing and knife coating can be used.

The green foils produced are laminated, arranged and cut according to the desired number of layers in the desired order in order to produce a layer block. In the case of producing a battery of the parallel type or series parallel type, it is preferable that arrangement and overlap take place such that the end face of the positive electrode layer and the end face of the negative electrode layer are inconsistent.

When manufacturing the layer block, the active material units described below can be manufactured to produce the layer block.

In this method, the solid electrolyte paste is first coated onto a PET film using a doctor blade in order to form a film. After a solid electrolyte sheet is obtained, the paste for the positive electrode active material layer is printed and dried on the solid electrolyte sheet by using a screen printing method. Then the paste for the positive electrode current collector layer is printed by means of screen printing and dried thereon. The paste for the positive electrode active material layer is further printed by screen printing and dried thereon, and then the unit of positive electrode active material is obtained by peeling off the PET film. In this way, a unit of positive electrode active material is obtained in which the paste for the positive electrode active material layer, the paste for the positive electrode current collector layer and the paste for the positive electrode active layer material are successively formed on the solid electrolyte sheet. In the same order, the negative electrode active material unit is made, and a negative electrode active material unit is obtained in which the negative electrode active material paste, the paste for the negative electrode current collector layer, and the negative electrode active material paste are sequentially formed on the solid electrolyte sheet.

A piece of the positive electrode active material unit and a piece of the negative electrode active material layer unit are laminated with the solid electrolyte sheet sandwiched between them. At this time, all of the units are stacked and laminated such that the paste of the positive electrode current collector layer of the first unit of positive electrode active material layers extends only to one end surface and the paste of the negative electrode current collector layer of the second unit of negative electrode active material layers extends only to the other end surface. The two sides of the laminated units are further laminated with a solid electrolyte sheet of a predetermined thickness to form a layer block.

The layer block produced is crimped once. The crimping takes place simultaneously with the heating. The heating temperature is set to, for example, 40 ° C ~ 95 ° C.

The crimped laminated block is heated to 500 ° C ~ 750 ° C for debinding, for example in a nitrogen, hydrogen or steam envelope. Then it is heated to 600 ° C ~ 1100 ° C in a nitrogen blanket and sintered. The sintering time is set to 0.1 to 3 hours, for example. The production of the laminate is completed with the sintering.

The relative density of the sintered laminate, the pair of electrode layers and the solid electrolyte layer arranged between the pair of electrode layers can be 80% or more. The relative density is higher, the diffusion transitions of movable ions in crystals can be connected more easily and the ion conductivity is improved.

Examples

example 1

The contents of the present invention are specifically described with reference to the examples and comparative examples, but the present invention is not limited to the following examples.

Production of positive electrode active material

In order to demonstrate the effect of the present embodiment, raw materials were weighed in such a way that Li / V in lithium vanadium phosphate was 1.55. Li ₂ CO ₃ , LiPO ₃ , V ₂ O ₃ and NH ₄ H ₂ PO _{4 were} used as starting materials. First, after weighing the starting materials using a ball mill (120 rpm / zirconium dioxide balls), mixing / comminution was carried out for 16 hours in ethanol. After separating and drying the powder mixture of the starting materials from the spheres and ethanol, this was calcined in a crucible made of magnesium oxide. To control the amount of bivalent V produced in lithium vanadium phosphate, calcination was carried out by changing the hydrogen content in a reduction envelope for 2 hours at 850 ° C. Thereafter, the calcined powder was treated using the ball mill (120 rpm / zirconia balls) for the purpose of grinding in ethanol for 16 hours. A lithium vanadium phosphate powder was obtained by separating and drying the comminuted powder from the spheres and ethanol. Based on the composition of lithium vanadium phosphate, it was confirmed by ICP that Li / V was 1.55. Further, based on the amount of bivalent V in V, it was confirmed by XPS that the amount of bivalent V in lithium vanadium phosphate was 5%.

Production of the negative electrode active material

The same powder as the positive electrode active material was used as the negative electrode active material.

Preparation of the paste for the positive electrode active material layer and the paste for the negative electrode active material layer

The paste for the layers of positive and negative electrode active material layers was prepared as follows: 15 parts of ethyl cellulose as a binder and 65 parts of dihydroterpineol as a solvent were placed in 100 parts of lithium vanadium phosphate powder, and mixing was carried out using a three-roller mixer and dispersion was performed to prepare the paste for the positive electrode active material layers and the negative electrode active material layers.

Production of the paste for the solid electrolyte layer

Li _f Al _g Ti _h P _i O _{j was} used as the solid _electrolyte (where f = 1.3, g = 0.3, h = 1.7, i = 3.0, j = 12.0), produced by use of the subsequent procedure. Li ₂ CO ₃ , Al ₂ O ₃ , TiO ₂ and NH ₄ H ₂ PO _{4 were} used as starting materials, ethanol was used as the solvent, and wet mixing was carried out by means of a ball mill for 16 hours. After the powder mixture of the starting materials had been separated and dried from the spheres and ethanol, calcination was carried out in a crucible made of aluminum oxide at 850 ° C. in the atmosphere for 2 hours. Thereafter, the calcined powder was treated for 16 hours in ethanol using the ball mill (120 rpm / zirconium dioxide balls) for the purpose of grinding. The crushed powder was separated from the balls and ethanol and dried to obtain the powder.

Then 100 parts of ethanol and 200 parts of toluene as a solvent were added to 100 parts of the powder using the ball mill, and wet mixing was carried out. Thereafter, 16 parts of polyvinyl butyral binder and 4.8 parts of benzyl butyl phthalate were added and mixed to prepare the paste for the solid electrolyte layer.

Production of the film for the solid electrolyte layer

The paste for the solid electrolyte layer was further processed to form a PET sheet film as a substrate by means of a doctor blade process in order to obtain the film for the solid electrolyte layer with a thickness of 15 μm.

Production of the paste for the positive electrode current collector layer and the paste for the negative electrode current collector layer

After mixing Cu powder and lithium vanadium phosphate powder in a weight ratio of 100: 9, 10 parts of ethyl cellulose as a binder and 50 parts of dihydroterpinol as a solvent were added, and mixing and dispersion were carried out using a three-roll mixer. to make the paste for the positive electrode current collector layer and the paste for the negative electrode current collector layer.

Production of the layer unit from active material

The paste for the electrode current collector layers with a thickness of 5 μm was printed on the film for the solid-state electrolyte layer using screen printing and then dried at 80 ° C. for 10 minutes. The paste for the positive electrode active material layer with a thickness of 5 µm was screen printed and then dried at 80 ° C for 10 minutes to obtain the positive electrode layer unit. On the other hand, the paste for the negative electrode active material layer with a thickness of 5 μm was printed on the film for the solid electrolyte layer using screen printing and then dried at 80 ° C. for 10 minutes. Then, the paste for the electrode current collector layer having a thickness of 5 µm was printed thereon using screen printing, and then dried for 10 minutes at 80 ° C to obtain the unit of negative electrode layers. Then the PET film was peeled off.

Production of the laminate

The unit of positive electrode layers, the unit of negative electrode layers, and the film for the solid electrolyte layer were used to obtain a laminated body by laminating such that the solid electrolyte layer, the positive electrode current collector layer, the positive electrode active material layer, the solid electrolyte layer, the negative electrode active material layer, the negative Electrode current collector layer and the solid electrolyte layer are formed in succession. At this time, all of the units are alternately stacked such that the positive electrode current collector layer of the positive electrode layer unit extends only to one end surface and the negative electrode current collector layer of the unit of negative electrode active material layers extends only to the other end surface. This was followed by hot crimping and then cut to length to produce the laminate.

Production of the sintered body

After debinding of the laminate obtained, sintering was carried out at the same time in order to obtain the sintered body. The debinding was carried out by heating to the sintering temperature of 700 ° C at a rate of 50 ° C / h in nitrogen, and maintaining this temperature for 10 hours. The simultaneous sintering was carried out by heating to the sintering temperature of 850 ° C at a rate of 200 ° C / h in nitrogen, and holding this temperature for 1 hour, and then it was naturally cooled after the sintering. The apparent size of the battery after simultaneous sintering was 3.2 mm * 2.5 mm * 0.4 mm.

Evaluation of the charging / discharging properties

As for the laminate obtained, the loading / unloading capacity was determined by means of a loading / unloading tester which was installed in the clamp, which was fastened by means of pins with springs. As the determination conditions, a determination was carried out at a charge / discharge current of 2 μA and a voltage of 0 V ~ 1.8V. The determined discharge capacity is shown in Table 1. The threshold value of sufficient discharge properties when used was 2.5 µAh.

Example 2

In this example, raw materials were weighed so that Li / V of lithium vanadium phosphate was 1.70, and the lithium vanadium phosphate powder was prepared by the same method as in Example 1. As for the composition of lithium vanadium Concerning phosphate, it was confirmed by ICP that Li / V was 1.70. Further, with respect to the amount of bivalent V contained in V, it was confirmed by XPS that the amount of bivalent V in the lithium vanadium phosphate was 20%. After the laminate was produced by the same method as in Example 1, debinding and sintering were carried out using the same method. The discharge properties of the laminate were evaluated using the same method as in Example 1. The discharge capacity determined is shown in Table 1.

Example 3

In this example, the raw materials were weighed so that Li / V of lithium vanadium phosphate was 1.80, and the lithium vanadium phosphate powder was prepared by the same method as in Example 1. What is the composition of lithium Concerning vanadium phosphate, ICP confirmed that Li / V was 1.80. Further, with regard to the amount of bivalent V contained in V, it was confirmed by XPS that the amount of bivalent V in the lithium vanadium phosphate was 33%. After the laminate was produced by the same method as in Example 1, debinding and sintering were carried out using the same method. The discharge properties of the laminate were evaluated using the same method as in Example 1. The discharge capacity determined is shown in Table 1.

Example 4

In this example, the raw materials were weighed so that Li / V of lithium vanadium phosphate was 1.93, and the lithium vanadium phosphate powder was prepared by the same method as in Example 1. What is the composition of lithium Concerning vanadium phosphate, it was confirmed by ICP that Li / V was 1.93. Further, the amount of bivalent V contained in V was increased is confirmed by XPS that the amount of bivalent V in the lithium vanadium phosphate was 49%. After the laminate was produced by the same method as in Example 1, debinding and sintering were carried out using the same method. The discharge properties of the laminate were evaluated using the same method as in Example 1. The discharge capacity determined is shown in Table 1.

Example 5

In this example, the raw materials were weighed so that Li / V of lithium vanadium phosphate was 2.30, and the lithium vanadium phosphate powder was prepared by the same method as in Example 1. What is the composition of lithium Concerning vanadium phosphate, ICP confirmed that Li / V was 2.30. Further, with respect to the amount of bivalent V contained in V, it was confirmed by XPS that the amount of bivalent V in the lithium vanadium phosphate was 78%. After the laminate was produced by the same method as in Example 1, debinding and sintering were carried out using the same method. The discharge properties of the laminate were evaluated using the same method as in Example 1. The discharge capacity determined is shown in Table 1.

Comparative Example 1

In this comparative example, the raw materials were weighed out so that Li / V of lithium vanadium phosphate was 1.48, and the lithium vanadium phosphate powder was prepared by the same method as in Example 1. What is the composition of lithium Concerning vanadium phosphate, it was confirmed by ICP that Li / V was 1.48. Further, with respect to the amount of bivalent V contained in V, it was confirmed by XPS that the amount of bivalent V in the lithium vanadium phosphate was 1%. After the laminate was produced by the same method as in Example 1, debinding and sintering were carried out using the same method. The discharge properties of the laminate were evaluated using the same method as in Example 1. The discharge capacity determined is shown in Table 1.

Comparative Example 2

In this comparative example, the raw materials were weighed out so that Li / V of lithium vanadium phosphate was 2.60, and the lithium vanadium phosphate powder was prepared by the same method as in Example 1. As for the composition of lithium Concerning vanadium phosphate, ICP confirmed that Li / V was 2.60. Further, with respect to the amount of bivalent V contained in V, it was confirmed by XPS that the amount of bivalent V in the lithium vanadium phosphate was 85%. After the laminate was produced by the same method as in Example 1, debinding and sintering were carried out using the same method. The discharge properties of the laminate were evaluated using the same method as in Example 1. The discharge capacity determined is shown in Table 1.

Comparative Example 3

In this comparative example, the raw materials were weighed out so that Li / V of lithium vanadium phosphate was 1.00, and the lithium vanadium phosphate powder was prepared by the same method as in Example 1. As for the composition of lithium Concerning vanadium phosphate, it was confirmed by ICP that Li / V was 1.00. Further, with respect to the amount of bivalent V contained in V, it was confirmed by XPS that the amount of bivalent V in the lithium vanadium phosphate was 20%. After the laminate was produced by the same method as in Example 1, debinding and sintering were carried out using the same method. The discharge properties of the laminate were evaluated using the same method as in Example 1. The discharge capacity determined is shown in Table 1.

Comparative Example 4

In this comparative example, the raw materials were weighed out so that Li / V of lithium vanadium phosphate was 2.00, and the lithium vanadium phosphate powder was produced by the same method as in Example 1. What is the composition of lithium Concerning vanadium phosphate, it was confirmed by ICP that Li / V was 2.00. Further, with respect to the amount of bivalent V contained in V, it was confirmed by XPS that the amount of bivalent V in the lithium vanadium phosphate was 1%. After the laminate was produced by the same method as in Example 1, debinding and sintering were carried out using the same method. The discharge properties of the laminate were evaluated using the same method as in Example 1. The discharge capacity determined is shown in Table 1.

Table 1 shows that the all-solid-state battery in which the lithium vanadium phosphate with Li / V and bivalent V is used in the range specified in the present invention for the layer of active material , can achieve a significantly higher discharge capacity.
Table 1 Li / V Bivalent V (%) Li _f Al _g Ti _h P _i O _j Discharge capacity of the manufactured battery (µAh) f G H i j example 1 1.55 5 1.30 0.30 1.70 3.00 12,00 4.82 Example 2 1.70 20 1.30 0.30 1.70 3.00 12,00 5.82 Example 3 1.80 33 1.30 0.30 1.70 3.00 12,00 5.86 Example 4 1.93 49 1.30 0.30 1.70 3.00 12,00 5.70 Example 5 2.30 78 1.30 0.30 1.70 3.00 12,00 4.28 See example 1 1.48 1 1.30 0.30 1.70 3.00 12,00 2.45 See example 2 2.60 85 1.30 0.30 1.70 3.00 12,00 2.38 See example 3 1.00 20 1.30 0.30 1.70 3.00 12,00 1.75 See example 4 2.00 1 1.30 0.30 1.70 3.00 12,00 2.10

Example 6

Production of positive electrode active material

In order to demonstrate the effect of the present embodiment, the raw materials were weighed in such a way that Li / V in lithium vanadium phosphate was 1.80. Li ₂ CO ₃ , LiPO ₃ , V ₂ O ₃ and NH ₄ H ₂ PO _{4 were} used as starting materials. First, using a ball mill (120 rpm / zirconium dioxide balls), after weighing the starting materials, mixing / comminution was carried out for 16 hours in ethanol. After separating and drying the powder mixture of the starting materials from the spheres and ethanol, this was calcined in a crucible made of magnesium oxide. To control the amount of bivalent V produced in lithium vanadium phosphate, calcination was carried out by changing the hydrogen content in a reduction envelope for 2 hours at 850 ° C. Thereafter, the calcined powder was treated using the ball mill (120 rpm / zirconia balls) for the purpose of grinding in ethanol for 16 hours. A lithium vanadium phosphate powder was obtained by separating and drying the comminuted powder from the spheres and ethanol. Based on the composition of lithium vanadium phosphate, it was confirmed by ICP that Li / V was 1.80. Further, based on the amount of bivalent V in V, it was confirmed by XPS that the amount of bivalent V in lithium vanadium phosphate was 33%.

Production of the negative electrode active material

The same powder as the positive electrode active material was used as the negative electrode active material.

Preparation of the paste for the positive electrode active material layer and the paste for the negative electrode active material layer

The paste for the positive and negative electrode active material layers was prepared as follows: 15 parts of ethyl cellulose as a binder and 65 parts of dihydroterpineol as a solvent were placed in 100 parts of lithium vanadium phosphate powder, and was carried out using a three-roller mixer Mix and disperse to make the paste for the positive and negative electrode active material layers.

Production of the paste for the solid electrolyte layer

As for the lithium aluminum titanium phosphate used as the solid electrolyte, it was weighed in such a way that f = 1.02, g = 0.13, h = 1.91, i = 3.0, j = 12.03 in the composition of Li _f Al _g Ti _h P _i O _j . Li ₂ CO ₃ , Al ₂ O ₃ , TiO ₂ and NH ₄ H ₂ PO _{4 were} used as starting materials, ethanol was used as the solvent, and wet mixing was carried out by means of a ball mill for 16 hours. After separating and drying the powder mixture of the starting materials from the spheres and ethanol, calcination was carried out in a crucible made of aluminum oxide at 850 ° C. in the atmosphere for 2 hours. After that, the calcined powder was treated for 16 hours in ethanol using the ball mill (120 rpm / zirconium dioxide balls) for the purpose of grinding. The crushed powder was separated from the balls and ethanol and dried to obtain the powder.

Then 100 parts of ethanol and 200 parts of toluene as a solvent were added to 100 parts of the powder using the ball mill, and wet mixing was carried out. Thereafter, 16 parts of polyvinyl butyral binder and 4.8 parts of benzyl butyl phthalate were added and mixed to prepare the paste for the solid electrolyte layer.

The paste for the solid electrolyte layer was further processed to form a PET sheet film as a substrate by means of a doctor blade process in order to obtain the film for the solid electrolyte layer with a thickness of 15 μm.

Production of the paste for the positive electrode current collector layer and the paste for the negative electrode current collector layer

After mixing Cu powder and lithium vanadium phosphate powder in a weight ratio of 100: 9, 10 parts of ethyl cellulose as a binder and 50 parts of dihydroterpinol as a solvent were added, and mixing and dispersion were carried out using a three-roll mixer. to make the paste for the current collector layers.

Manufacture of the unit from active layer material

The paste for the positive electrode current collector layer with a thickness of 5 μm was printed on the film for the solid electrolyte layer using screen printing and then dried at 80 ° C. for 10 minutes. The paste for the positive electrode active material layer with a thickness of 5 µm was screen printed, and then dried for 10 minutes at 80 ° C to obtain the unit of positive electrode layers. On the other hand, the paste for the negative electrode active material layer with a thickness of 5 μm was printed on the film for the solid electrolyte layer using screen printing and then dried at 80 ° C. for 10 minutes. Then, the paste for the negative electrode current collector layer having a thickness of 5 µm was printed thereon using screen printing, and then dried for 10 minutes at 80 ° C to obtain the negative electrode layer unit. Then the PET film was peeled off.

Production of the laminate

The unit of positive electrode layers, the unit of negative electrode layers, and the film for the solid electrolyte layer were used to obtain a laminated body by laminating such that the solid electrolyte layer, the positive electrode current collector layer, the positive electrode active material layer, the solid electrolyte layer, the negative electrode active material layer, the negative Electrode current collector layer and the solid electrolyte layer were formed in succession. At this time, all of the units are alternately layered such that the positive electrode current collector layer of the positive electrode layer unit has only extended to one end surface and the negative electrode current collector layer of the negative electrode layer unit has only extended to the other end surface. This was followed by hot crimping and then cut to length to produce the laminate.

Production of the sintered body

After the binder had been debindered, sintering was carried out at the same time in order to obtain the sintered body. The debinding was carried out by heating to the sintering temperature of 700 ° C at a rate of 50 ° C / h in nitrogen, and maintaining this temperature for 10 hours. The simultaneous sintering was carried out by heating to the sintering temperature of 850 ° C at a rate of 200 ° C / h in nitrogen, and holding this temperature for 1 hour, and then it was naturally cooled after the sintering. The apparent size of the battery after simultaneous sintering was 3.2 mm * 2.5 mm * 0.4 mm.

Evaluation of the charging / discharging properties

As for the laminate obtained, the loading / unloading capacity was determined by means of a loading / unloading tester which was installed in the clamp, which was fastened by means of pins with springs. As a determination condition, a determination was carried out at a charge / discharge current of 2 µA and a voltage of 0 V ~ 1.8 V. The discharge capacity determined is shown in Table 2. The threshold value of sufficient discharge properties when used was 2.5 µAh.

Example 7

Preparation of positive electrode active material and negative electrode active material

To check the effect of the present embodiment, raw materials were weighed out so that Li / V in the lithium vanadium phosphate was 1.80 and lithium vanadium phosphate powder was obtained using the same procedure as in Example 6 Further, the lithium vanadium phosphate powder was used to prepare the paste for the positive and negative electrode active materials using the same procedure as in Example 6.

Production of the paste for the solid electrolyte layer

As for the lithium aluminum titanium phosphate used as the solid electrolyte, it was weighed in such a way that f = 1.5, g = 0.5, h = 1.5, i = 3.0, j = 12.0 in the composition of Li _f Al _g Ti _h P _i O _j . Li ₂ CO ₃ , Al ₂ O ₃ , TiO ₂ and NH ₄ H ₂ PO _{4 were} used as starting materials, ethanol was used as the solvent, and wet mixing was carried out by means of a ball mill for 16 hours. After the powder mixture of the starting materials had been separated and dried from the spheres and ethanol, calcination was carried out in a crucible made of aluminum oxide at 850 ° C. in the atmosphere for 2 hours. The calcined powder was then treated for 16 hours in ethanol using the ball mill (120 rpm / zirconium dioxide) for the purpose of grinding. The crushed powder was separated from the balls and ethanol and dried to obtain the powder. Furthermore, after the production of the laminated body, debinding and sintering were carried out using the same method as in Example 6. The discharge properties of the laminate were evaluated using the same method as in Example 6. The discharge capacity determined is shown in Table 2.

Example 8

Preparation of positive electrode active material and negative electrode active material

To check the effect of the present embodiment, raw materials were weighed so that Li / V in the lithium vanadium phosphate was 1.80, and lithium vanadium phosphate powder was obtained using the same procedure as in Example 6. Furthermore, the lithium vanadium phosphate powder was used to prepare the paste for the positive and negative electrode active materials by the same method as in Example 6.

Production of the paste for the solid electrolyte layer

As for the lithium aluminum titanium phosphate used as the solid electrolyte, it was weighed in such a manner that f = 2.0, g = 1.0, h = 1.0, i = 3.0, j = 12.0 in the composition of Li _f Al _g Ti _h P _i O _j . Li ₂ CO ₃ , Al ₂ O ₃ , TiO ₂ and NH ₄ H ₂ PO _{4 were} used as starting materials, ethanol was used as solvent, and wet mixing was carried out for 16 hours using a ball mill. After separating and drying the powder mixture of the starting materials from the balls and ethanol was for 2 hours calcined in a crucible made of alumina at 850 ° C in the atmosphere. After that, the calcined powder was treated for 16 hours in ethanol using the ball mill (120 rpm / zirconium dioxide balls) for the purpose of grinding. The crushed powder was separated from the balls and ethanol and dried to obtain the powder. Furthermore, after the production of the laminated body, debinding and sintering were carried out using the same method as in Example 6. The discharge properties of the laminate were evaluated using the same method as in Example 6. The discharge capacity determined is shown in Table 2.

Example 9

Preparation of positive electrode active material and negative electrode active material

To check the effect of the present embodiment, raw materials were weighed so that Li / V in the lithium vanadium phosphate was 1.80, and lithium vanadium phosphate powder was obtained using the same procedure as in Example 6. Further, the lithium vanadium phosphate powder was used to prepare the paste for the positive and negative electrode active materials using the same procedure as in Example 6.

Production of the paste for the solid electrolyte layer

As for the lithium aluminum titanium phosphate used as the solid electrolyte, it was weighed in such a way that f = 2.1, g = 1.1, h = 0.9, i = 3.0, j = 12.0 in the composition of Li _f Al _g Ti _h P _i O _j . Li ₂ CO ₃ , Al ₂ O ₃ , TiO ₂ and NH ₄ H ₂ PO _{4 were} used as starting materials, ethanol was used as the solvent, and wet mixing was carried out by means of a ball mill for 16 hours. After the powder mixture of the starting materials had been separated and dried from the spheres and ethanol, calcination was carried out in a crucible made of aluminum oxide at 850 ° C. in the atmosphere for 2 hours. After that, the calcined powder was treated for 16 hours in ethanol using the ball mill (120 rpm / zirconium dioxide balls) for the purpose of grinding. The crushed powder was separated from the balls and ethanol and dried to obtain the powder. Furthermore, after the production of the laminated body, debinding and sintering were carried out using the same method as in Example 6. The discharge properties of the laminate were evaluated using the same method as in Example 6. The discharge capacity determined is shown in Table 2.

Example 10

Preparation of positive electrode active material and negative electrode active material

To check the effect of the present embodiment, raw materials were weighed so that Li / V in the lithium vanadium phosphate was 1.80, and lithium vanadium phosphate powder was obtained using the same procedure as in Example 6. Further, the lithium vanadium phosphate powder was used to prepare the paste for the positive and negative electrode active materials using the same procedure as in Example 6.

Production of the paste for the solid electrolyte layer

As for the lithium aluminum titanium phosphate used as the solid electrolyte, it was weighed in such a way that f = 0.5, g = 0.02, h = 1.0, i = 2.8, j = 9.28 in the composition of Li _f Al _g Ti _h P _i O _j . Li ₂ CO ₃ , Al ₂ O ₃ , TiO ₂ and NH ₄ H ₂ PO _{4 were} used as starting materials, ethanol was used as solvent, and wet mixing was carried out for 16 hours using a ball mill. After the powder mixture of the starting materials had been separated and dried from the spheres and ethanol, calcination was carried out in a crucible made of aluminum oxide at 850 ° C. in the atmosphere for 2 hours. After that, the calcined powder was treated for 16 hours in ethanol using the ball mill (120 rpm / zirconium dioxide balls) for the purpose of grinding. The crushed powder was separated from the balls and ethanol and dried to obtain the powder. Furthermore, after the production of the laminated body using the same method as in Example 6, debinding and sintering were carried out using the same method. The discharge properties of the laminate were evaluated using the same method as in Example 6. The discharge capacity determined is shown in Table 2.

Example 11

Preparation of positive electrode active material and negative electrode active material

To check the effect of the present embodiment, raw materials were weighed so that Li / V in the lithium vanadium phosphate was 1.80 and obtained using the same procedure as in Example 6 lithium vanadium phosphate powder. Further, the lithium vanadium phosphate powder was used to prepare the paste for the positive and negative electrode active materials using the same procedure as in Example 6.

Production of the paste for the solid electrolyte layer

As for the lithium aluminum titanium phosphate used as the solid electrolyte, it was weighed in such a way that f = 0.5, g = 0.02, h = 2.0, i = 3.2, j = 12.28 in the composition of Li _f Al _g Ti _h P _i O _j . Li ₂ CO ₃ , Al ₂ O ₃ , TiO ₂ and NH ₄ H ₂ PO _{4 were} used as starting materials, ethanol was used as the solvent, and wet mixing was carried out by means of a ball mill for 16 hours. After the powder mixture of the starting materials had been separated and dried from the spheres and ethanol, calcination was carried out in a crucible made of aluminum oxide at 850 ° C. in the atmosphere for 2 hours. After that, the calcined powder was treated for 16 hours in ethanol using the ball mill (120 rpm / zirconium dioxide balls) for the purpose of grinding. The crushed powder was separated from the balls and ethanol and dried to obtain the powder. Furthermore, after the production of the laminated body, debinding and sintering were carried out using the same method as in Example 6. The discharge properties of the laminate were evaluated using the same method as in Example 6. The discharge capacity determined is shown in Table 2.

Example 12

Preparation of positive electrode active material and negative electrode active material

To check the effect of the present embodiment, raw materials were weighed out so that Li / V in the lithium vanadium phosphate was 1.80, and lithium vanadium phosphate powder was obtained using the same procedure as in Example 6. Further, the lithium vanadium phosphate powder was used to prepare the paste for the positive and negative electrode active materials using the same procedure as in Example 6.

Production of the paste for the solid electrolyte layer

As for the lithium aluminum titanium phosphate used as the solid electrolyte, it was weighed in such a way that f = 0.5, g = 1.0, h = 1.0, i = 2.8, j = 10.75 in the composition of Li _f Al _g Ti _h P _i O _j . Li ₂ CO ₃ , Al ₂ O ₃ , TiO ₂ and NH ₄ H ₂ PO _{4 were} used as starting materials, ethanol was used as the solvent, and wet mixing was carried out by means of a ball mill for 16 hours. After the powder mixture of the starting materials had been separated and dried from the spheres and ethanol, calcination was carried out in a crucible made of aluminum oxide at 850 ° C. in the atmosphere for 2 hours. After that, the calcined powder was treated for 16 hours in ethanol using the ball mill (120 rpm / zirconium dioxide balls) for the purpose of grinding. The crushed powder was separated from the balls and ethanol and dried to obtain the powder. Furthermore, after the production of the laminated body using the same method as in Example 6, debinding and sintering were carried out using the same method. The discharge properties of the laminate were evaluated using the same method as in Example 6. The discharge capacity determined is shown in Table 2.

Example 13

Preparation of positive electrode active material and negative electrode active material

To check the effect of the present embodiment, raw materials were weighed out so that Li / V in the lithium vanadium phosphate was 1.80, and lithium vanadium phosphate powder was obtained using the same procedure as in Example 6. Further, the lithium vanadium phosphate powder was used to prepare the paste for the positive and negative electrode active materials using the same procedure as in Example 6.

Production of the paste for the solid electrolyte layer

As for the lithium aluminum titanium phosphate used as the solid electrolyte, it was weighed in such a way that f = 0.5, g = 1.0, h = 2.0, i = 3.2, j = 13.75 in the composition of Li _f Al _g Ti _h P _i O _j . Li ₂ CO ₃ , Al ₂ O ₃ , TiO ₂ and NH ₄ H ₂ PO _{4 were} used as starting materials, ethanol was used as the solvent, and wet mixing was carried out by means of a ball mill for 16 hours. After separating and drying the powder mixture of the starting materials from the spheres and ethanol, calcination was carried out in a crucible made of aluminum oxide at 850 ° C. in the atmosphere for 2 hours. After that, the calcined powder was treated for 16 hours in ethanol using the ball mill (120 rpm / zirconium dioxide balls) for the purpose of grinding. The crushed powder was separated from the balls and ethanol and dried to obtain the powder. Furthermore, after the production of the laminated body using the same method as in Example 6, debinding and sintering were carried out using the same method. The discharge properties of the laminate were evaluated using the same method as in Example 6. The discharge capacity determined is shown in Table 2.

Example 14

Preparation of positive electrode active material and negative electrode active material

To check the effect of the present embodiment, raw materials were weighed out so that Li / V in the lithium vanadium phosphate was 1.80, and lithium vanadium phosphate powder was obtained using the same procedure as in Example 6. Further, the lithium vanadium phosphate powder was used to prepare the paste for the positive and negative electrode active materials using the same procedure as in Example 6.

Production of the paste for the solid electrolyte layer

As for the lithium aluminum titanium phosphate used as the solid electrolyte, it was weighed in such a way that f = 3.0, g = 0.1, h = 1.0, i = 2.8, j = 10.65 in the composition of Li _f Al _g Ti _h P _i O _j . Li ₂ CO ₃ , Al ₂ O ₃ , TiO ₂ and NH ₄ H ₂ PO _{4 were} used as starting materials, ethanol was used as the solvent, and wet mixing was carried out by means of a ball mill for 16 hours. After the powder mixture of the starting materials had been separated and dried from the spheres and ethanol, calcination was carried out in a crucible made of aluminum oxide at 850 ° C. in the atmosphere for 2 hours. After that, the calcined powder was treated for 16 hours in ethanol using the ball mill (120 rpm / zirconium dioxide balls) for the purpose of grinding. The crushed powder was separated from the balls and ethanol and dried to obtain the powder. Furthermore, after the production of the laminated body using the same method as in Example 6, debinding and sintering were carried out using the same method. The discharge properties of the laminate were evaluated using the same method as in Example 6. The discharge capacity determined is shown in Table 2.

Example 15

Preparation of positive electrode active material and negative electrode active material

To check the effect of the present embodiment, raw materials were weighed out so that Li / V in the lithium vanadium phosphate was 1.80, and lithium vanadium phosphate powder was obtained using the same procedure as in Example 6. Further, the lithium vanadium phosphate powder was used to prepare the paste for the positive and negative electrode active materials using the same procedure as in Example 6.

Production of the paste for the solid electrolyte layer

As for the lithium aluminum titanium phosphate used as the solid electrolyte, it was weighed in such a way that f = 3.0, g = 0.1, h = 2.0, i = 3.2, j = 13.65 in the composition of Li _f Al _g Ti _h P _i O _j . Li ₂ CO ₃ , Al ₂ O ₃ , TiO ₂ and NH ₄ H ₂ PO _{4 were} used as starting materials, ethanol was used as the solvent, and wet mixing was carried out by means of a ball mill for 16 hours. After the powder mixture of the starting materials had been separated and dried from the spheres and ethanol, calcination was carried out in a crucible made of aluminum oxide at 850 ° C. in the atmosphere for 2 hours. After that, the calcined powder was treated for 16 hours in ethanol using the ball mill (120 rpm / zirconium dioxide balls) for the purpose of grinding. The crushed powder became from the balls and ethanol and dried to obtain the powder. Furthermore, after the production of the laminated body using the same method as in Example 6, debinding and sintering were carried out using the same method. The discharge properties of the laminate were evaluated using the same method as in Example 6. The discharge capacity determined is shown in Table 2.

Example 16

Preparation of positive electrode active material and negative electrode active material

To check the effect of the present embodiment, raw materials were weighed out so that Li / V in the lithium vanadium phosphate was 1.80, and lithium vanadium phosphate powder was obtained using the same procedure as in Example 6. Further, the lithium vanadium phosphate powder was used to prepare the paste for the positive and negative electrode active materials using the same procedure as in Example 6.

Production of the paste for the solid electrolyte layer

As for the lithium aluminum titanium phosphate used as the solid electrolyte, it was weighed in such a manner that f = 3.0, g = 1.0, h = 1.0, i = 2.8, j = 12.0 in the composition of Li _f Al _g Ti _h P _i O _j . Li ₂ CO ₃ , Al ₂ O ₃ , TiO ₂ and NH ₄ H ₂ PO _{4 were} used as starting materials, ethanol was used as the solvent, and wet mixing was carried out by means of a ball mill for 16 hours. After the powder mixture of the starting materials had been separated and dried from the spheres and ethanol, calcination was carried out in a crucible made of aluminum oxide at 850 ° C. in the atmosphere for 2 hours. After that, the calcined powder was treated for 16 hours in ethanol using the ball mill (120 rpm / zirconium dioxide balls) for the purpose of grinding. The crushed powder was separated from the balls and ethanol and dried to obtain the powder. Furthermore, after the production of the laminated body using the same method as in Example 6, debinding and sintering were carried out using the same method. The discharge properties of the laminate were evaluated using the same method as in Example 6. The discharge capacity determined is shown in Table 2.

Example 17

Preparation of positive electrode active material and negative electrode active material

To check the effect of the present embodiment, raw materials were weighed out so that Li / V in the lithium vanadium phosphate was 1.80, and lithium vanadium phosphate powder was obtained using the same procedure as in Example 6. Further, the lithium vanadium phosphate powder was used to prepare the paste for the positive and negative electrode active materials using the same procedure as in Example 6.

Production of the paste for the solid electrolyte layer

As for the lithium aluminum titanium phosphate used as the solid electrolyte, it was weighed in such a way that f = 3.0, g = 1.0, h = 2.0, i = 3.2 j = 15.0 in the composition of Li _f Al _g Ti _h P _i O _j . Li ₂ CO ₃ , Al ₂ O ₃ , TiO ₂ and NH ₄ H ₂ PO _{4 were} used as starting materials, ethanol was used as the solvent, and wet mixing was carried out by means of a ball mill for 16 hours. After the powder mixture of the starting materials had been separated and dried from the spheres and ethanol, calcination was carried out in a crucible made of aluminum oxide at 850 ° C. in the atmosphere for 2 hours. After that, the calcined powder was treated for 16 hours in ethanol using the ball mill (120 rpm / zirconium dioxide balls) for the purpose of grinding. The crushed powder was separated from the balls and ethanol and dried to obtain the powder. Furthermore, after the production of the laminated body using the same method as in Example 6, debinding and sintering were carried out using the same method. The discharge properties of the laminate were evaluated using the same method as in Example 6. The discharge capacity determined is shown in Table 2.

Comparative Example 5

Preparation of positive electrode active material and negative electrode active material

As a comparative example, raw materials were weighed out so that Li / V in lithium vanadium phosphate was 1.48, and a lithium vanadium phosphate powder was obtained. Further, the lithium vanadium phosphate powder was used to prepare the paste for the positive and negative electrode active materials using the same procedure as in Example 6.

Production of the paste for the solid electrolyte layer

As for the lithium aluminum titanium phosphate used as the solid electrolyte, it was weighed in such a way that f = 1.02, g = 0.13, h = 1.91, i = 3.0 j = 12.03 in the composition of Li _f Al _g Ti _h P _i O _j . Li ₂ CO ₃ , Al ₂ O ₃ , TiO ₂ and NH ₄ H ₂ PO _{4 were} used as starting materials, ethanol was used as the solvent, and wet mixing was carried out by means of a ball mill for 16 hours. After the powder mixture of the starting materials had been separated and dried from the spheres and ethanol, calcination was carried out in a crucible made of aluminum oxide at 850 ° C. in the atmosphere for 2 hours. After that, the calcined powder was treated for 16 hours in ethanol using the ball mill (120 rpm / zirconium dioxide balls) for the purpose of grinding. The crushed powder was separated from the balls and ethanol and dried to obtain the powder. Furthermore, after the production of the laminated body using the same method as in Example 6, debinding and sintering were carried out using the same method. The discharge properties of the laminate were evaluated using the same method as in Example 6. The discharge capacity determined is shown in Table 2.

Comparative Example 6

Preparation of positive electrode active material and negative electrode active material

As a comparative example, raw materials were weighed so that Li / V in lithium vanadium phosphate was 1.48, and a lithium vanadium phosphate powder was obtained by the same procedure as in Example 6. Further, the lithium vanadium phosphate powder was used to prepare the paste for the positive and negative electrode active materials using the same procedure as in Example 6.

Production of the paste for the solid electrolyte layer

As for the lithium aluminum titanium phosphate used as the solid electrolyte, it was weighed in such a way that f = 1.5, g = 0.5, h = 1.5, i = 3.0, j = 12.0 in the composition of Li _f Al _g Ti _h P _i O _j . Li ₂ CO ₃ , Al ₂ O ₃ , TiO ₂ and NH ₄ H ₂ PO _{4 were} used as starting materials, ethanol was used as the solvent, and wet mixing was carried out by means of a ball mill for 16 hours. After the powder mixture of the starting materials had been separated and dried from the spheres and ethanol, calcination was carried out in a crucible made of aluminum oxide at 850 ° C. in the atmosphere for 2 hours. After that, the calcined powder was treated for 16 hours in ethanol using the ball mill (120 rpm / zirconium dioxide balls) for the purpose of grinding. The crushed powder was separated from the balls and ethanol and dried to obtain the powder. Furthermore, after the production of the laminated body using the same method as in Example 6, debinding and sintering were carried out using the same method. The discharge properties of the laminate were evaluated using the same method as in Example 6. The discharge capacity determined is shown in Table 2.

Comparative Example 7

Preparation of positive electrode active material and negative electrode active material

As a comparative example, raw materials were weighed so that Li / V in lithium vanadium phosphate was 1.48, and a lithium vanadium phosphate powder was obtained by the same procedure as in Example 6. Further, the lithium vanadium phosphate powder was used to prepare the paste for the positive and negative electrode active materials using the same procedure as in Example 6.

Production of the paste for the solid electrolyte layer

As for the lithium aluminum titanium phosphate used as the solid electrolyte, it was weighed in such a manner that f = 2.0, g = 1.0, h = 1.0, i = 3.0 j = 12.0 in the composition of Li _f Al _g Ti _h P _i O _j . Li ₂ CO ₃ , Al ₂ O ₃ , TiO ₂ and NH ₄ H ₂ PO _{4 were} used as starting materials, ethanol was used as the solvent, and wet mixing was carried out by means of a ball mill for 16 hours. After the powder mixture of the starting materials had been separated and dried from the spheres and ethanol, calcination was carried out in a crucible made of aluminum oxide at 850 ° C. in the atmosphere for 2 hours. After that, the calcined powder was treated for 16 hours in ethanol using the ball mill (120 rpm / zirconium dioxide balls) for the purpose of grinding. The crushed powder was separated from the balls and ethanol and dried to obtain the powder. Furthermore, after the production of the laminated body using the same method as in Example 6, debinding and sintering were carried out using the same method. The discharge properties of the laminate were evaluated using the same method as in Example 6. The determined discharge capacity is shown in Table 2.

Comparative Example 8

Preparation of positive electrode active material and negative electrode active material

As a comparative example, raw materials were weighed so that Li / V in lithium vanadium phosphate was 1.48, and a lithium vanadium phosphate powder was obtained by the same procedure as in Example 6. Further, the lithium vanadium phosphate powder was used to prepare the paste for the positive and negative electrode active materials using the same procedure as in Example 6.

Production of the paste for the solid electrolyte layer

As for the lithium aluminum titanium phosphate used as the solid electrolyte, it was weighed in such a way that f = 0.5, g = 0.02, h = 1.0, i = 2.8, j = 9.28 in the composition of Li _f Al _g Ti _h P _i O _j . Li ₂ CO ₃ , Al ₂ O ₃ , TiO ₂ and NH ₄ H ₂ PO _{4 were} used as starting materials, ethanol was used as the solvent, and wet mixing was carried out by means of a ball mill for 16 hours. After the powder mixture of the starting materials had been separated and dried from the spheres and ethanol, calcination was carried out in a crucible made of aluminum oxide at 850 ° C. in the atmosphere for 2 hours. After that, the calcined powder was treated for 16 hours in ethanol using the ball mill (120 rpm / zirconium dioxide balls) for the purpose of grinding. The crushed powder was separated from the balls and ethanol and dried to obtain the powder. Furthermore, after the production of the laminated body using the same method as in Example 6, debinding and sintering were carried out using the same method. The discharge properties of the laminate were evaluated using the same method as in Example 6. The discharge capacity determined is shown in Table 2.

Comparative Example 9

Preparation of positive electrode active material and negative electrode active material

As a comparative example, raw materials were weighed so that Li / V in lithium vanadium phosphate was 1.48, and a lithium vanadium phosphate powder was obtained by the same procedure as in Example 6. Further, the lithium vanadium phosphate powder was used to prepare the paste for the positive and negative electrode active materials using the same procedure as in Example 6.

Production of the paste for the solid electrolyte layer

As for the lithium aluminum titanium phosphate used as the solid electrolyte, it was weighed in such a way that f = 0.5, g = 1.0, h = 2.0, i = 3.2, j = 13.75 in the composition of Li _f Al _g Ti _h P _i O _j . Li ₂ CO ₃ , Al ₂ O ₃ , TiO ₂ and NH ₄ H ₂ PO _{4 were} used as starting materials, ethanol was used as the solvent, and wet mixing was carried out by means of a ball mill for 16 hours. After the powder mixture of the starting materials had been separated and dried from the spheres and ethanol, calcination was carried out in a crucible made of aluminum oxide at 850 ° C. in the atmosphere for 2 hours. After that, the calcined powder was treated for 16 hours in ethanol using the ball mill (120 rpm / zirconium dioxide balls) for the purpose of grinding. The crushed powder became from the balls and ethanol and dried to obtain the powder. Furthermore, after the production of the laminated body using the same method as in Example 6, debinding and sintering were carried out using the same method. The discharge properties of the laminate were evaluated using the same method as in Example 6. The discharge capacity determined is shown in Table 2.

Comparative Example 10

Preparation of positive electrode active material and negative electrode active material

As a comparative example, raw materials were weighed so that Li / V in lithium vanadium phosphate was 1.48, and a lithium vanadium phosphate powder was obtained by the same procedure as in Example 6. Further, the lithium vanadium phosphate powder was used to prepare the paste for the positive and negative electrode active materials using the same procedure as in Example 6.

Production of the paste for the solid electrolyte layer

As for the lithium aluminum titanium phosphate used as the solid electrolyte, it was weighed in such a way that f = 3.0, g = 0.1, h = 1.0, i = 2.8, j = 10.65 in the composition of Li _f Al _g Ti _h P _i O _j . Li ₂ CO ₃ , Al ₂ O ₃ , TiO ₂ and NH ₄ H ₂ PO _{4 were} used as starting materials, ethanol was used as the solvent, and wet mixing was carried out by means of a ball mill for 16 hours. After the powder mixture of the starting materials had been separated and dried from the spheres and ethanol, calcination was carried out in a crucible made of aluminum oxide at 850 ° C. in the atmosphere for 2 hours. After that, the calcined powder was treated for 16 hours in ethanol using the ball mill (120 rpm / zirconium dioxide balls) for the purpose of grinding. The crushed powder was separated from the balls and ethanol and dried to obtain the powder. Furthermore, after the production of the laminated body using the same method as in Example 6, debinding and sintering were carried out using the same method. The discharge properties of the laminate were evaluated using the same method as in Example 6. The discharge capacity determined is shown in Table 2.

Comparative Example 11

Preparation of positive electrode active material and negative electrode active material

As a comparative example, raw materials were weighed so that Li / V in lithium vanadium phosphate was 1.48, and a lithium vanadium phosphate powder was obtained by the same procedure as in Example 6. Further, the lithium vanadium phosphate powder was used to prepare the paste for the positive and negative electrode active materials using the same procedure as in Example 6.

Production of the paste for the solid electrolyte layer

As for the lithium aluminum titanium phosphate used as the solid electrolyte, it was weighed in such a way that f = 3.0, g = 1.0 h = 2.0, i = 3.2, j = 15.0 in the composition of Li _f Al _g Ti _h P _i O _j . Li ₂ CO ₃ , Al ₂ O ₃ , TiO ₂ and NH ₄ H ₂ PO _{4 were} used as starting materials, ethanol was used as the solvent, and wet mixing was carried out by means of a ball mill for 16 hours. After the powder mixture of the starting materials had been separated and dried from the spheres and ethanol, calcination was carried out in a crucible made of aluminum oxide at 850 ° C. in the atmosphere for 2 hours. After that, the calcined powder was treated for 16 hours in ethanol using the ball mill (120 rpm / zirconium dioxide balls) for the purpose of grinding. The crushed powder was separated from the balls and ethanol and dried to obtain the powder. Furthermore, after the production of the laminated body using the same method as in Example 6, debinding and sintering were carried out using the same method. The discharge properties of the laminate were evaluated using the same method as in Example 6. The discharge capacity determined is shown in Table 2.

Table 2 shows that the all-solid-state battery, in which the lithium aluminum titanium phosphate is used as a solid electrolyte, in the situation that the lithium vanadium phosphate with Li / V and bivalent V used in the area used in the present invention in the layer of active material, can achieve a particularly high discharge capacity.
Table 2 Li / V Bivalent V (%) Li _f Al _g Ti _h P _i O _j Discharge capacity of the manufactured battery (µAη) (µAh) f G H i j Example 6 1.80 33 1.02 0.13 1.91 3.00 12.03 4.98 Example 7 1.80 33 1.50 0.50 1.50 3.00 12,00 3.81 Example 8 1.80 33 2.00 1.00 1.00 3.00 12,00 2.65 Example 9 1.80 33 2.10 1.10 0.90 3.00 12,00 2.57 Example 10 1.80 33 0.50 0.02 1.00 2.00 9.28 2.99 Example 11 1.80 33 0.50 0.02 2.00 3.20 12.28 3.24 Example 12 1.80 33 0.50 1.00 1.00 2.80 10.75 2.78 Example 13 1.80 33 0.50 1.00 2.00 3.20 13.75 2.53 Example 14 1.80 33 3.00 0.10 1.00 2.80 10.65 2.83 Example 15 1.80 33 3.00 0.10 2.00 3.20 13.65 2.52 Example 16 1.80 33 3.00 1.00 1.00 2.80 12,00 2.70 Example 17 1.80 33 3.00 1.00 2.00 3.20 15.00 2.54 Comp Bsp.5 1.48 1 1.02 0.13 1.91 3.00 12.03 1.61 Comp Bsp.6 1.48 1 1.50 0.50 1.50 3.00 12,00 1.23 Comp Bsp.7 1.48 1 2.00 1.00 1.00 3.00 12,00 0.76 Comp Bsp.8 1.48 1 0.50 0.02 1.00 2.80 9.28 1.05 Comp Bsp.9 1.48 1 0.50 1.00 2.00 3.20 13.75 0.88 Comp Bsp.10 1.48 1 3.00 0.10 1.00 2.80 10.65 0.99 Comp Bsp.11 1.48 1 3.00 1.00 2.00 3.20 15.00 0.89

Example 18

Production of positive electrode active material

In order to demonstrate the effect of the present embodiment, the raw materials were weighed in such a way that Li / V in lithium vanadium phosphate was 1.93. Li ₂ CO ₃ , LiPO ₃ , V ₂ O ₃ and NH ₄ H ₂ PO _{4 were} used as starting materials. First, after weighing the raw materials, mixing / crushing for 16 hours in ethanol was carried out using a ball mill (120 rpm / zirconia balls). After separating and drying the powder mixture of the starting materials from the spheres and ethanol, this was calcined in a crucible made of magnesium oxide. To control the amount of bivalent V produced in lithium vanadium phosphate, calcination was carried out by changing the hydrogen content in a reduction envelope for 2 hours at 850 ° C. Thereafter, the calcined powder was treated in ethanol for 16 hours using the ball mill (120 rpm / zirconia balls) for the purpose of grinding. A lithium vanadium phosphate powder was obtained by separating and drying the comminuted powder from the spheres and ethanol. Based on the composition of lithium vanadium phosphate, it was confirmed by ICP that Li / V was 1.93. Further, based on the amount of bivalent V in V, it was confirmed by XPS that the amount of bivalent V in lithium vanadium phosphate was 49%.

Production of the negative electrode active material

In order to demonstrate the effect of the present embodiment, the raw materials were weighed out so that Li / V in lithium vanadium phosphate was 1.70. Li ₂ CO ₃ , LiPO ₃ , V ₂ O ₃ and NH ₄ H ₂ PO _{4 were} used as starting materials. First, after weighing the raw materials, mixing / crushing for 16 hours in ethanol was carried out using a ball mill (120 rpm / zirconia balls). After separating and drying the powder mixture of the starting materials from the spheres and ethanol, this was calcined in a crucible made of magnesium oxide. To control the amount of bivalent V produced in lithium vanadium phosphate, calcination was carried out by changing the hydrogen content in a reduction envelope for 2 hours at 850 ° C. Thereafter, the calcined powder was treated in ethanol for 16 hours using the ball mill (120 rpm / zirconia balls) for the purpose of grinding. A lithium vanadium phosphate powder was obtained by separating and drying the crushing powder from the spheres and ethanol. Based on the composition of lithium vanadium phosphate, it was confirmed by ICP that Li / V was 1.70. Further, based on the amount of bivalent V in V, it was confirmed by XPS that the amount of bivalent V in lithium vanadium phosphate was 20%.

Preparation of the paste for the positive electrode active material layer

The paste for the positive electrode active material layer was prepared using lithium vanadium phosphate powder with Li / V of 1.93 and an amount of bivalent V of 49%. The paste for the positive electrode active material layer was prepared as follows: 15 parts of ethyl cellulose as a binder and 65 parts of dihydroterpineol as a solvent were placed in 100 parts of lithium vanadium phosphate powder, and mixing and dispersion were carried out using a three-roll mixer. to make the paste for the positive electrode active material layers.

Preparation of the paste for the negative electrode active material layer

The paste for the negative electrode active material layer was prepared using lithium vanadium phosphate powder with Li / V of 1.70 and an amount of bivalent V of 20%. The paste for the negative electrode active material layer was prepared as follows: 15 parts of ethyl cellulose as a binder and 65 parts of dihydroterpineol as a solvent were placed in 100 parts of lithium vanadium phosphate powder, and mixing and dispersion were carried out using a three-roller mixer, to make the paste for the negative electrode active material layer.

Production of the paste for the solid electrolyte layer

As for the lithium aluminum titanium phosphate used as the solid electrolyte, it was weighed in such a way that f = 1.3, g = 0.3, h = 1.7, i = 3.0, j = 12.0 in the composition of Li _f Al _g Ti _h P _i O _j . Li ₂ CO ₃ , Al ₂ O ₃ , TiO ₂ and NH ₄ H ₂ PO _{4 were} used as starting materials, ethanol was used as the solvent, and wet mixing was carried out by means of a ball mill for 16 hours. After the powder mixture of the starting materials had been separated and dried from the spheres and ethanol, calcination was carried out in a crucible made of aluminum oxide at 850 ° C. in the atmosphere for 2 hours. Thereafter, the calcined powder was treated for 16 hours in ethanol using the ball mill (120 rpm / zirconia balls) for the purpose of grinding. The crushed powder was separated from the balls and ethanol and dried to obtain the powder.

Then 100 parts of ethanol and 200 parts of toluene as a solvent were added to 100 parts of the powder using the ball mill, and wet mixing was carried out. Thereafter, 16 parts of polyvinyl butyral binder and 4.8 parts of benzyl butyl phthalate were added and mixed to prepare the paste for the solid electrolyte layer.

The paste for the solid electrolyte layer was further processed to form a PET sheet film as a substrate using a doctor blade method to obtain the film for the solid electrolyte layer with a thickness of 15 μm.

Production of the paste for the positive electrode current collector layer and the paste for the negative electrode current collector layer

After mixing Cu powder used as the positive electrode current collector and lithium vanadium phosphate powder with Li / V of 1.93 and mixing the Cu powder used as negative electrode current collector and lithium Vanadium phosphate powder with Li / V of 1.70 according to a weight ratio of 100: 9, 10 parts of ethyl cellulose as a binder and 50 parts of dihydroterpinol as a solvent were added, and mixing and dispersion were carried out using a three-roll mixer to obtain the Make paste for the positive electrode current collector layer and the paste for the negative electrode current collector layer.

Manufacture of the unit from active layer material

The paste for the positive electrode current collector layer with a thickness of 5 µm was printed on the film for the solid electrolyte layer using screen printing, and then dried at 80 ° C for 10 minutes. The paste for the positive electrode active material layer with a thickness of 5 µm was screen printed, and then dried for 10 minutes at 80 ° C to obtain the unit of positive electrode layers. On the other hand, the paste for the negative electrode active material layer was printed with a thickness of 5 µm on the film for the solid electrolyte layer using screen printing, and then dried at 80 ° C for 10 minutes. Then, the paste for the negative electrode current collector layer was printed on it with a thickness of 5 µm using screen printing, and then dried for 10 minutes at 80 ° C to obtain the negative electrode layer unit. Then the PET film was peeled off.

Production of the laminate

The unit of positive electrode layers, the unit of negative electrode layers, and the film for the solid electrolyte layer were used to obtain a laminate by laminating such that the solid electrolyte layer, the positive electrode current collector layer, the positive electrode active material layer, the solid electrolyte layer, the negative electrode active material layer negative electrode current collector layer and the solid electrolyte layer were formed in succession. At this time, all of the units are alternately stacked such that the positive electrode current collector layer of the positive electrode layer unit extends only to one end surface and the negative electrode current collector layer of the unit of negative electrode active material layers extends only to the other end surface. Thereafter, hot crimping was carried out, and then cutting was carried out to produce the laminated body.

Production of the sintered body

After debinding of the obtained laminate, sintering was carried out simultaneously to obtain the sintered body. The debinding was carried out by heating to the sintering temperature of 700 ° C at a rate of 50 ° C / h in nitrogen, and maintaining this temperature for 10 hours. The simultaneous sintering was carried out by heating to the sintering temperature of 850 ° C at a rate of 200 ° C / h in nitrogen, and holding this temperature for 1 hour, and then it was naturally cooled after the sintering. The apparent size of the battery after simultaneous sintering was 3.2 mm * 2.5 mm * 0.4 mm.

Evaluation of the charging / discharging properties

As for the laminate obtained, the loading / unloading capacity was determined by means of a loading / unloading tester which was installed in the clamp, which was fastened by means of pins with springs. As determination conditions, a determination was carried out with a charge / discharge current of 2 µA and a voltage of 0V ~ 1.8V. The discharge capacity determined is shown in Table 3. The threshold value of sufficient discharge properties when used was 2.5 µAh.

Example 19

In this example, raw materials for the paste for the positive electrode active material layer and the paste for the positive electrode current collector layer were weighed out such that Li / V of lithium vanadium phosphate was 2.30. Furthermore, raw materials for the paste for the negative electrode current collector layer were weighed in such that Li / V of lithium vanadium phosphate was 1.55. For these materials, a lithium vanadium phosphate powder was made using the same procedure as in Example 18. As for the composition of the lithium vanadium phosphate, it was confirmed by ICP that Li / V was 2.30 and 1.55. Further, with respect to the amount of bivalent V contained in V, it was confirmed by XPS that the amount of bivalent V in the lithium vanadium phosphate was 78% and 5%. After the laminate was produced by the same procedure as in Example 18, debinding and sintering were carried out by the same procedure. The discharge properties of the laminate were evaluated using the same method as in Example 18. The discharge capacity determined is shown in Table 3.

Example 20

In this example, raw materials for the paste for the positive electrode active material layer and the paste for the positive electrode current collector layer were weighed out such that Li / V of lithium vanadium phosphate was 2.30. Furthermore, raw materials for the paste for the negative electrode active material layer and the paste for the negative electrode current collector layer were weighed in such a way that Li / V of lithium vanadium phosphate was 1.80. For these materials, a lithium vanadium phosphate powder was made using the same procedure as in Example 18. As for the composition of the lithium vanadium phosphate, it was confirmed by ICP that Li / V was 2.30 and 1.80. Further, with respect to the amount of bivalent V contained in V, it was confirmed by XPS that the amount of bivalent V in the lithium vanadium phosphate was 78% and 33%. After the laminate was produced by the same procedure as in Example 18, debinding and sintering were carried out by the same procedure. The discharge properties of the laminate were evaluated using the same method as in Example 18. The discharge capacity determined is shown in Table 3.

Example 21

In this example, raw materials for the paste for the positive electrode active material layer and the paste for the positive electrode current collector layer were weighed in such a way that Li / V of lithium vanadium phosphate was 1.70. Furthermore, raw materials for the paste for the negative electrode active material layer and the paste for the negative electrode current collector layer were weighed in such a way that Li / V of lithium vanadium phosphate was 1.55. For these materials, a lithium vanadium phosphate powder was made using the same procedure as in Example 18. As for the composition of the lithium vanadium phosphate, it was confirmed by ICP that Li / V was 1.70 and 1.55. Furthermore, with respect to the amount of bivalent V contained in V, it was confirmed by XPS that the amount of bivalent V in the lithium vanadium phosphate was 20% and 5%. After the laminate was produced by the same procedure as in Example 18, debinding and sintering were carried out by the same procedure. The discharge properties of the laminate were evaluated using the same method as in Example 18. The discharge capacity determined is shown in Table 3.

Comparative Example 12

In this comparative example, raw materials for the paste for the positive electrode active material layer and the paste for the positive electrode current collector layer were weighed in such that Li / V of lithium vanadium phosphate was 2.60. Furthermore, for the paste for the negative electrode active material layer and the paste for the negative electrode current collector layer, raw materials were weighed in such a way that Li / V of lithium vanadium phosphate was 1.48. For these materials, a lithium vanadium phosphate powder was made using the same procedure as in Example 18. As for the composition of the lithium vanadium phosphate, ICP confirmed that Li / V was 2.60 and 1.48. Further, with respect to the amount of bivalent V contained in V, it was confirmed by XPS that the amount of bivalent V in the lithium vanadium phosphate was 85% and 1%. After the laminate was produced by the same procedure as in Example 18, debinding and sintering were carried out by the same procedure. The discharge properties of the laminate were evaluated using the same method as in Example 18. The discharge capacity determined is shown in Table 3.

Comparative Example 13

In this comparative example, raw materials for the paste for the positive electrode active material layer and the paste for the positive electrode current collector layer were weighed in such a way that Li / V of lithium vanadium phosphate was 1.80. Furthermore, for the paste for the negative electrode active material layer and the paste for the negative electrode current collector layer, raw materials were weighed in such a way that Li / V of lithium vanadium phosphate was 1.48. For these materials, a lithium vanadium phosphate powder was made using the same procedure as in Example 18. As for the composition of the lithium vanadium phosphate, it was confirmed by ICP that Li / V was 1.80 and 1.48. Further, with respect to the amount of bivalent V contained in V, it was confirmed by XPS that the amount of bivalent V in the lithium vanadium phosphate was 33% and 1%. After the laminate was produced by the same procedure as in Example 18, debinding and sintering were carried out by the same procedure. The discharge properties of the laminate were evaluated using the same method as in Example 18. The discharge capacity determined is shown in Table 3.

Table 3 shows that the all-solid-state battery in which the lithium vanadium phosphate with Li / V or bivalent V is in the range specified in the present invention for the positive electrode active material layer and the negative electrode active material layer as a solid electrolyte can be used, can achieve a sufficiently high discharge capacity.
Table 3 Positive electrode: Li / V Positive electrode: proportion of bivalent V (%) Negative electrode: Li / V Negative electrode: proportion of bivalent V Li _f Al _g Ti _h P _i O _j Charging capacity of the manufactured battery (µAh) f G H i j Example 18 1.93 49 1.70 20 1.30 0.30 1.70 3.00 12,00 6.91 Example 19 2.30 78 1.55 5 1.30 0.30 1.70 3.00 12,00 5.46 Example 20 2.30 78 1.80 33 1.30 0.30 1.70 3.00 12,00 6.08 Example 21 1.70 20 1.55 5 1.30 0.30 1.70 3.00 12,00 6.38 See Example 12 2.60 85 1.48 1 1.30 0.30 1.70 3.00 12,00 1.33 See Example 13 1.80 33 1.48 1 1.30 0.30 1.70 3.00 12,00 2.29

Example 22

Production of positive electrode active material

In order to demonstrate the effect of the present embodiment, the raw materials were weighed in such a way that Li / V in lithium vanadium phosphate was 2.30. Li ₂ CO ₃ , LiPO ₃ , V ₂ O ₃ and NH ₄ H ₂ PO _{4 were} used as starting materials. First, after weighing the raw materials, mixing / crushing for 16 hours in ethanol was carried out using a ball mill (120 rpm / zirconia balls). After separating and drying the powder mixture of the starting materials from the spheres and ethanol, this was calcined in a crucible made of magnesium oxide. To the amount of To control the equivalent V generated in lithium vanadium phosphate, a calcination was carried out by changing the hydrogen content in a reduction envelope for 2 hours at 850 ° C. Thereafter, the calcined powder was treated in ethanol for 16 hours using the ball mill (120 rpm / zirconia balls) for the purpose of grinding. A lithium vanadium phosphate powder was obtained by separating and drying the comminuted powder from the spheres and ethanol. Based on the composition of lithium vanadium phosphate, it was confirmed by ICP that Li / V was 2.30. Further, based on the amount of bivalent V in V, it was confirmed by XPS that the amount of bivalent V in each lithium vanadium phosphate was 78%.

Production of the negative electrode active material

In order to demonstrate the effect of the present embodiment, the raw materials were weighed in such a way that Li / V in lithium vanadium phosphate was 1.80. Li ₂ CO ₃ , LiPO ₃ , V ₂ O ₃ and NH ₄ H ₂ PO _{4 were} used as starting materials. First, after weighing the raw materials, mixing / crushing for 16 hours in ethanol was carried out using a ball mill (120 rpm / zirconia balls). After separating and drying the powder mixture of the starting materials from the spheres and ethanol, this was calcined in a crucible made of magnesium oxide. To control the amount of bivalent V produced in lithium vanadium phosphate, calcination was carried out by changing the hydrogen content in a reduction envelope for 2 hours at 850 ° C. Thereafter, the calcined powder was treated in ethanol for 16 hours using the ball mill (120 rpm / zirconia balls) for the purpose of grinding. A lithium vanadium phosphate powder was obtained by separating and drying the comminuted powder from the spheres and ethanol. Based on the composition of lithium vanadium phosphate, it was confirmed by ICP that Li / V was 1.80. Further, based on the amount of bivalent V in V, it was confirmed by XPS that the amount of bivalent V in each lithium vanadium phosphate was 33%.

Preparation of the paste for the positive electrode active material layer

The paste for the positive electrode active material layer was prepared using lithium vanadium phosphate powder with Li / V of 2.30 and an amount of bivalent V of 78%. The paste for the positive electrode active material layer was prepared as follows: 15 parts of ethyl cellulose as a binder and 65 parts of dihydroterpineol as a solvent were placed in 100 parts of lithium vanadium phosphate powder, and mixing and dispersion were carried out using a three-roll mixer. to make the paste for the positive electrode active material layer.

Preparation of the paste for the negative electrode active material layer

The paste for the negative electrode active material layer was prepared using lithium vanadium phosphate powder with Li / V of 1.80 and an amount of bivalent V of 33%. The paste for the negative electrode active material layer was prepared as follows: 15 parts of ethyl cellulose as a binder and 65 parts of dihydroterpineol as a solvent were placed in 100 parts of lithium vanadium phosphate powder, and mixing and dispersion were carried out using a three-roller mixer, to make the paste for the negative electrode active material layer.

Production of the paste for the solid electrolyte layer

As for the lithium aluminum titanium phosphate used as the solid electrolyte, it was weighed in such a way that f = 1.02, g = 0.13, h = 1.91, i = 3.0, j = 12.03 in the composition of Li _f Al _g Ti _h P _i O _j . Li ₂ CO ₃ , Al ₂ O ₃ , TiO ₂ and NH ₄ H ₂ PO _{4 were} used as starting materials, ethanol was used as the solvent, and wet mixing was carried out by means of a ball mill for 16 hours. After the powder mixture of the starting materials had been separated and dried from the spheres and ethanol, calcination was carried out in a crucible made of aluminum oxide at 850 ° C. in the atmosphere for 2 hours. Thereafter, the calcined powder was treated for 16 hours in ethanol using the ball mill (120 rpm / zirconia balls) for the purpose of grinding. The crushed powder was separated from the balls and ethanol and dried to obtain the powder.

Then 100 parts of ethanol and 200 parts of toluene as a solvent were added to 100 parts of the powder using the ball mill, and wet mixing was carried out. Thereafter, 16 parts of polyvinyl butyral binder and 4.8 parts of benzyl butyl phthalate were added and mixed to prepare the paste for the solid electrolyte layer.

The paste for the solid electrolyte layer was further processed to form a PET sheet film as a substrate using a doctor blade method to obtain the film for the solid electrolyte layer with a thickness of 15 μm.

Preparation of the paste for the positive electrode current collector layer and the paste for the negative electrode current collector layer

After mixing Cu powder used as the positive electrode current collector and lithium vanadium phosphate powder with Li / V of 2.30 and mixing the Cu powder used as the negative electrode current collector and lithium Vanadium phosphate powder with Li / V of 1.80 according to a weight ratio of 100: 9, 10 parts of ethyl cellulose as a binder and 50 parts of dihydroterpinol as a solvent were added, and mixing and dispersion were carried out using a three-roll mixer to obtain the Make paste for the positive electrode current collector layer and the paste for the negative electrode current collector layer.

Manufacture of the unit from active layer material

The paste for the positive electrode current collector layer with a thickness of 5 µm was printed on the film for the solid electrolyte layer using screen printing, and then dried at 80 ° C for 10 minutes. The paste for the positive electrode active material layer with a thickness of 5 µm was screen printed, and then dried for 10 minutes at 80 ° C to obtain the unit of positive electrode layers. On the other hand, the paste for the negative electrode active material layer was printed with a thickness of 5 µm on the film for the solid electrolyte layer using screen printing, and then dried for 10 minutes at 80 ° C, and then the paste for the negative electrode current collector layer with a thickness of Printed 5 µm on them using screen printing, and then dried for 10 minutes at 80 ° C to obtain the unit of negative electrode layers. Then the PET film was peeled off.

Production of the laminate

The positive electrode layer unit, the negative electrode layer unit, and the film for the solid electrolyte layer were used to obtain a laminated body by laminating such that the solid electrolyte layer, the positive electrode current collector layer, the positive electrode active material layer, the solid electrolyte layer, the negative electrode active material layer negative electrode current collector layer and the solid electrolyte layer were formed in succession. At this time, all of the units are alternately stacked such that the positive electrode current collector layer of the positive electrode layer unit extends only to one end surface and the negative electrode current collector layer of the unit of negative electrode active material layers extends only to the other end surface. Thereafter, hot crimping was carried out, and then cutting was carried out to produce the laminated body.

Production of the sintered body

After debinding of the obtained laminate, sintering was carried out simultaneously to obtain the sintered body. Debinding was carried out by heating to the sintering temperature of 700 ° C at a rate of 50 ° C / h in nitrogen, and holding this temperature for 10 hours. The simultaneous sintering was carried out by heating to the sintering temperature of 850 ° C at a rate of 200 ° C / h in nitrogen, and holding this temperature for 1 hour, and then it was naturally cooled after the sintering. The apparent size of the battery after simultaneous sintering was 3.2 mm * 2.5 mm * 0.4 mm.

Evaluation of the charging / discharging properties

As for the laminate obtained, the loading / unloading capacity was determined by means of a loading / unloading tester which was installed in the clamp, which was fastened by means of pins with springs. As determination conditions, a determination was carried out with a charge / discharge current of 2 µA and a voltage of 0V ~ 1.8V. The discharge capacity determined is shown in Table 4. The threshold value of sufficient discharge properties when used was 2.5 µAh.

Example 23

Preparation of positive electrode active material and negative electrode active material

In this example, raw materials for the paste for the positive electrode active material layer and the paste for the positive electrode current collector layer were weighed out such that Li / V of lithium vanadium phosphate was 2.30. Furthermore, raw materials for the paste for the negative electrode active material layer and the paste for the negative electrode current collector layer were weighed in such a way that Li / V of lithium vanadium phosphate was 1.80. For these materials, a lithium vanadium phosphate powder was made using the same procedure as in Example 22. As for the composition of the lithium vanadium phosphate, it was confirmed by ICP that Li / V was 2.30 and 1.80. Further, with respect to the amount of bivalent V contained in V, it was confirmed by XPS that the amount of bivalent V in the lithium vanadium phosphate was 78% and 33%.

Preparation of the paste for the positive electrode active material layer and the paste for the negative electrode active material layer

Lithium vanadium phosphate powder with Li / V of 2.30 and lithium vanadium phosphate powder with Li / V of 1.80 were used to use the paste for the positive electrode active material layer and the paste for the negative electrode active material layer the same procedure as in Example 22.

Production of the paste for the solid electrolyte layer

As for the lithium aluminum titanium phosphate used as the solid electrolyte, it was weighed in such a way that f = 1.5, g = 0.5, h = 1.5, i = 3.0, j = 12.0 in the composition of Li _f Al _g Ti _h P _i O _j . Li ₂ CO ₃ , Al ₂ O ₃ , TiO ₂ and NH ₄ H ₂ PO _{4 were} used as starting materials, ethanol was used as the solvent, and wet mixing was carried out by means of a ball mill for 16 hours. After the powder mixture of the starting materials had been separated and dried from the spheres and ethanol, calcination was carried out in a crucible made of aluminum oxide at 850 ° C. in the atmosphere for 2 hours. Thereafter, the calcined powder was treated for 16 hours in ethanol using the ball mill (120 rpm / zirconia balls) for the purpose of grinding. The crushed powder was separated from the balls and ethanol and dried to obtain the powder.

Production of the solid electrolyte foil

The lithium aluminum titanium phosphate powder obtained was used to produce the sheet for the solid electrolyte sheet using the same procedure as in Example 22.

Production of the paste for the positive electrode current collector layer and the paste for the negative electrode current collector layer

To prepare the paste for the positive electrode current collector layer and the paste for the negative electrode current collector layer, lithium vanadium phosphate powder with Li / V of 2.30, lithium vanadium phosphate powder with Li / V of 1.80 and Cu were used Powder using the same procedure used in Example 22.

Fabrication of Unit of Active Layer Material and Fabrication of Laminate Using the same procedure as in Example 22, the paste for the positive electrode active material layer and the paste for the positive electrode current collector layer were used to make the unit of positive electrode layers, and the paste for the negative electrode active material layer and the paste for the negative electrode current collector layer were used to make the negative electrode layer unit. Further, the film for the solid electrolyte layer, the positive electrode layer unit, and the negative electrode layer unit were used to produce the layered body using the same method as in Example 22.

Production of the sintered body

After debinding of the obtained laminate, sintering was carried out simultaneously to obtain the sintered body. Debinding was carried out by heating to the sintering temperature of 700 ° C at a rate of 50 ° C / h in nitrogen, and holding this temperature for 10 hours. The simultaneous sintering was carried out by heating to the sintering temperature of 850 ° C at a rate of 200 ° C / h in nitrogen, and holding this temperature for 1 hour, and then it was naturally cooled after the sintering. The apparent size of the battery after simultaneous sintering was 3.2 mm * 2.5 mm * 0.4 mm.

Evaluation of the charging / discharging properties

As for the laminate obtained, the loading / unloading capacity was determined by means of a loading / unloading tester which was installed in the clamp, which was fastened by means of pins with springs. As a determination condition, a determination was carried out at a charge / discharge current of 2 µA and a voltage of 0 V ~ 1.8 V. The discharge capacity determined is shown in Table 4. The threshold value of sufficient discharge properties when used was 2.5 µAh.

Example 24

Preparation of positive electrode active material and negative electrode active material

In this example, raw materials for the paste for the positive electrode active material layer and the paste for the positive electrode current collector layer were weighed out such that Li / V of lithium vanadium phosphate was 2.30. Furthermore, raw materials for the paste for the negative electrode active material layer and the paste for the negative electrode current collector layer were weighed in such a way that Li / V of lithium vanadium phosphate was 1.80. For these materials, a lithium vanadium phosphate powder was made using the same procedure as in Example 22. As for the composition of the lithium vanadium phosphate, it was confirmed by ICP that Li / V was 2.30 and 1.80. Further, with respect to the amount of bivalent V contained in V, it was confirmed by XPS that the amount of bivalent V in the lithium vanadium phosphate was 78% and 33%.

Preparation of the paste for the positive electrode active material layer and the paste for the negative electrode active material layer

Lithium vanadium phosphate powder with Li / V of 2.30 and lithium vanadium phosphate powder with Li / V of 1.80 were used to prepare the paste for the positive electrode active material layer and the paste for the negative electrode active material layer same procedure as used in Example 22.

Production of the paste for the solid electrolyte layer

As for the lithium aluminum titanium phosphate used as the solid electrolyte, it was weighed in such a manner that f = 2.0, g = 1.0, h = 1.0, i = 3.0, j = 12.0 in the composition of Li _f Al _g Ti _h P _i O _j . Li ₂ CO ₃ , Al ₂ O ₃ , TiO ₂ and NH ₄ H ₂ PO _{4 were} used as starting materials, ethanol was used as the solvent, and wet mixing was carried out by means of a ball mill for 16 hours. After the powder mixture of the starting materials had been separated and dried from the spheres and ethanol, calcination was carried out in a crucible made of aluminum oxide at 850 ° C. in the atmosphere for 2 hours. Thereafter, the calcined powder was treated for 16 hours in ethanol using the ball mill (120 rpm / zirconium dioxide balls) for the purpose of grinding. The crushed powder was separated from the balls and ethanol and dried to obtain the powder.

Production of the solid electrolyte foil

The lithium aluminum titanium phosphate powder obtained was used to produce the solid electrolyte sheet using the same procedure as in Example 22.

Production of the paste for the positive electrode current collector layer and the paste for the negative electrode current collector layer

To prepare the paste for the positive electrode current collector layer and the paste for the negative electrode current collector layer, lithium vanadium phosphate powder with Li / V of 2.30, lithium vanadium phosphate powder with Li / V of 1.80 and Cu were used Powder using the same procedure used in Example 22.

Fabrication of Unit of Active Layer Material and Fabrication of Laminate Using the same procedure as in Example 22, the paste for the positive electrode active material layer and the paste for the positive electrode current collector layer were used to make the unit of positive electrode layers, and the paste for the negative electrode active material layer and the paste for the negative electrode current collector layer were used to make the negative electrode layer unit. Further, the film for the solid electrolyte layer, the positive electrode layer unit, and the negative electrode layer unit were used to produce the layered body using the same method as in Example 22.

Production of the sintered body

After debinding of the obtained laminate, sintering was carried out simultaneously to obtain the sintered body. The debinding was carried out by heating to the sintering temperature of 700 ° C at a rate of 50 ° C / h in nitrogen, and maintain this temperature for 10 hours. The simultaneous sintering was done by heating to the sintering temperature of 850 ° C at a rate of 200 ° C / h in nitrogen, and holding this temperature for 1 hour, and then it was naturally cooled after the sintering. The apparent size of the battery after simultaneous sintering was 3.2 mm * 2.5 mm * 0.4 mm.

Evaluation of the charging / discharging properties

As for the laminate obtained, the loading / unloading capacity was determined by means of a loading / unloading tester which was installed in the clamp, which was fastened by means of pins with springs. As determination conditions, a determination was carried out with a charge / discharge current of 2 µA and a voltage of 0V ~ 1.8V. The discharge capacity determined is shown in Table 4. The threshold value of sufficient discharge properties when used was 2.5 µAh.

Example 25

Preparation of positive electrode active material and negative electrode active material

In this example, raw materials for the paste for the positive electrode active material layer and the paste for the positive electrode current collector layer were weighed out such that Li / V of lithium vanadium phosphate was 2.30. Furthermore, raw materials for the paste for the negative electrode active material layer and the paste for the negative electrode current collector layer were weighed in such a way that Li / V of lithium vanadium phosphate was 1.80. For these materials, a lithium vanadium phosphate powder was made using the same procedure as in Example 22. As for the composition of the lithium vanadium phosphate, it was confirmed by ICP that Li / V was 2.30 and 1.80. Further, with respect to the amount of bivalent V contained in V, it was confirmed by XPS that the amount of bivalent V in the lithium vanadium phosphate was 78% and 33%.

Preparation of the paste for the positive electrode active material layer and the paste for the negative electrode active material layer

Lithium vanadium phosphate powder with Li / V of 2.30 and lithium vanadium phosphate powder with Li / V of 1.80 were used to use the paste for the positive electrode active material layer and the paste for the negative electrode active material layer the same procedure as in Example 22.

Production of the paste for the solid electrolyte layer

As for the lithium aluminum titanium phosphate used as the solid electrolyte, it was weighed in such a way that f = 2.1, g = 1.1, h = 0.9, i = 3.0, j = 12.0 in the composition of Li _f Al _g Ti _h P _i O _j . Li ₂ CO ₃ , Al ₂ O ₃ , TiO ₂ and NH ₄ H ₂ PO _{4 were} used as starting materials, ethanol was used as the solvent, and wet mixing was carried out by means of a ball mill for 16 hours. After the powder mixture of the starting materials had been separated and dried from the spheres and ethanol, calcination was carried out in a crucible made of aluminum oxide at 850 ° C. in the atmosphere for 2 hours. Thereafter, the calcined powder was treated for 16 hours in ethanol using the ball mill (120 rpm / zirconium dioxide balls) for the purpose of grinding. The crushed powder was separated from the balls and ethanol and dried to obtain the powder.

Production of the solid electrolyte foil

The lithium aluminum titanium phosphate powder obtained was used to produce the solid electrolyte sheet using the same procedure as in Example 22.

Production of the paste for the positive electrode current collector layer and the paste for the negative electrode current collector layer

To produce the paste for the positive electrode current collector layer and the paste for the negative electrode current collector layer, lithium vanadium phosphate powder with Li / V of 2.30, lithium vanadium phosphate powder with Li / V of 1.80 and Cu were used Powder using the same procedure used in Example 15.

Fabrication of Active Layer Material Unit and Laminated Body Using the same procedure as in Example 22, the paste for the positive electrode active material layer and the paste for the positive electrode current collector layer were used to make the unit of positive electrode layers, and the paste for the negative electrode active material layer and the paste for the negative electrode current collector layer were used to make the negative electrode layer unit. Further, the film for the solid electrolyte layer, the positive electrode layer unit, and the negative electrode layer unit were used to produce the layered body using the same method as in Example 22.

Production of the sintered body

After debinding of the obtained laminate, sintering was carried out simultaneously to obtain the sintered body. Debinding was carried out by heating to the sintering temperature of 700 ° C at a rate of 50 ° C / h in nitrogen, and holding this temperature for 10 hours. The simultaneous sintering was carried out by heating to the sintering temperature of 850 ° C at a rate of 200 ° C / h in nitrogen, and holding this temperature for 1 hour, and then it was naturally cooled after the sintering. The apparent size of the battery after simultaneous sintering was 3.2 mm * 2.5 mm * 0.4 mm.

Evaluation of the charging / discharging properties

As for the laminate obtained, the loading / unloading capacity was determined by means of a loading / unloading tester which was installed in the clamp, which was fastened by means of pins with springs. As determination conditions, a determination was carried out with a charge / discharge current of 2 µA and a voltage of 0V ~ 1.8V. The discharge capacity determined is shown in Table 4. The threshold value of sufficient discharge properties when used was 2.5 µAh.

Example 26

Preparation of positive electrode active material and negative electrode active material

In this example, raw materials for the paste for the positive electrode active material layer and the paste for the positive electrode current collector layer were weighed out such that Li / V of lithium vanadium phosphate was 2.30. Furthermore, raw materials for the paste for the negative electrode active material layer and the paste for the negative electrode current collector layer were weighed in such a way that Li / V of lithium vanadium phosphate was 1.80. For these materials, a lithium vanadium phosphate powder was made using the same procedure as in Example 22. As for the composition of the lithium vanadium phosphate, it was confirmed by ICP that Li / V was 2.30 and 1.80. Further, with respect to the amount of bivalent V contained in V, it was confirmed by XPS that the amount of bivalent V in the lithium vanadium phosphate was 78% and 33%.

Preparation of the paste for the positive electrode active material layer and the paste for the negative electrode active material layer

Lithium vanadium phosphate powder with Li / V of 2.30 and lithium vanadium phosphate powder with Li / V of 1.80 were used to use the paste for the positive electrode active material layer and the paste for the negative electrode active material layer the same procedure as in Example 22.

Production of the paste for the solid electrolyte layer

As for the lithium aluminum titanium phosphate used as the solid electrolyte, it was weighed in such a way that f = 0.5, g = 0.02, h = 1.0, i = 2.8, j = 9.28 in the composition of Li _f Al _g Ti _h P _i O _j . Li ₂ CO ₃ , Al ₂ O ₃ , TiO ₂ and NH ₄ H ₂ PO _{4 were} used as starting materials, ethanol was used as the solvent, and wet mixing was carried out by means of a ball mill for 16 hours. After the powder mixture of the starting materials had been separated and dried from the spheres and ethanol, calcination was carried out in a crucible made of aluminum oxide at 850 ° C. in the atmosphere for 2 hours. Thereafter, the calcined powder was treated for 16 hours in ethanol using the ball mill (120 rpm / zirconium dioxide balls) for the purpose of grinding. The crushed powder was separated from the balls and ethanol and dried to obtain the powder.

Production of the solid electrolyte foil

The lithium aluminum titanium phosphate powder obtained was used to produce the solid electrolyte sheet using the same procedure as in Example 22.

Production of the paste for the positive electrode current collector layer and the paste for the negative electrode current collector layer

To produce the paste for the positive electrode current collector layer and the paste for the negative electrode current collector layer, lithium vanadium phosphate powder with Li / V of 2.30, lithium vanadium phosphate powder with Li / V of 1.80 and Cu were used Powder using the same procedure used in Example 22.

Fabrication of Unit of Active Layer Material and Fabrication of Laminate Using the same procedure as in Example 22, the paste for the positive electrode active material layer and the paste for the positive electrode current collector layer were used to make the unit of positive electrode layers, and the paste for the negative electrode active material layer and the paste for the negative electrode current collector layer were used to make the negative electrode layer unit. Further, the film for the solid electrolyte layer, the positive electrode layer unit, and the negative electrode layer unit were used to produce the layered body using the same method as in Example 22.

Production of the sintered body

After debinding of the obtained laminate, sintering was carried out simultaneously to obtain the sintered body. Debinding was carried out by heating to the sintering temperature of 700 ° C at a rate of 50 ° C / h in nitrogen, and holding this temperature for 10 hours. The simultaneous sintering was carried out by heating to the sintering temperature of 850 ° C at a rate of 200 ° C / h in nitrogen, and holding this temperature for 1 hour, and then it was naturally cooled after the sintering. The apparent size of the battery after simultaneous sintering was 3.2 mm * 2.5 mm * 0.4 mm.

Evaluation of the charging / discharging properties

As for the laminate obtained, the loading / unloading capacity was determined by means of a loading / unloading tester which was installed in the clamp, which was fastened by means of pins with springs. As determination conditions, a determination was carried out with a charge / discharge current of 2 µA and a voltage of 0V ~ 1.8V. The discharge capacity determined is shown in Table 4. The threshold value of sufficient discharge properties when used was 2.5 µAh.

Example 27

Preparation of positive electrode active material and negative electrode active material

In this example, raw materials for the paste for the positive electrode active material layer and the paste for the positive electrode current collector layer were weighed out such that Li / V of lithium vanadium phosphate was 2.30. Furthermore, raw materials for the paste for the negative electrode active material layer and the paste for the negative electrode current collector layer were weighed in such a way that Li / V of lithium vanadium phosphate was 1.80. For these materials, a lithium vanadium phosphate powder was made using the same procedure as in Example 22. As for the composition of the lithium vanadium phosphate, it was confirmed by ICP that Li / V was 2.30 and 1.80. Further, with respect to the amount of bivalent V contained in V, it was confirmed by XPS that the amount of bivalent V in the lithium vanadium phosphate was 78% and 33%.

Preparation of the paste for the positive electrode active material layer and the paste for the negative electrode active material layer

Lithium vanadium phosphate powder with Li / V of 2.30 and lithium vanadium phosphate powder with Li / V of 1.80 were used to make the paste for the positive electrode active material layer and the paste for the negative electrode active material layer using the same method as in Example 22.

Production of the paste for the solid electrolyte layer

As for the lithium aluminum titanium phosphate used as the solid electrolyte, it was weighed in such a way that f = 0.5, g = 0.02, h = 2.0, i = 3.2, j = 12.28 in the composition of Li _f Al _g Ti _h P _i O _j . Li ₂ CO ₃ , Al ₂ O ₃ , TiO ₂ and NH ₄ H ₂ PO _{4 were} used as starting materials, ethanol was used as the solvent, and wet mixing was carried out by means of a ball mill for 16 hours. After the powder mixture of the starting materials had been separated and dried from the spheres and ethanol, calcination was carried out in a crucible made of aluminum oxide at 850 ° C. in the atmosphere for 2 hours. Thereafter, the calcined powder was treated for 16 hours in ethanol using the ball mill (120 rpm / zirconium dioxide balls) for the purpose of grinding. The crushed powder was separated from the balls and ethanol and dried to obtain the powder.

Production of the solid electrolyte foil

The lithium aluminum titanium phosphate powder obtained was used to produce the solid electrolyte sheet using the same procedure as in Example 22.

Production of the paste for the positive electrode current collector layer and the paste for the negative electrode current collector layer

To produce the paste for the positive electrode current collector layer and the paste for the negative electrode current collector layer, lithium vanadium phosphate powder with Li / V of 2.30, lithium vanadium phosphate powder with Li / V of 1.80 and Cu were used Powder using the same procedure used in Example 22.

Production of the unit from active layer material and production of the laminate

Using the same procedure as in Example 22, the paste for the positive electrode active material layer and the paste for the positive electrode current collector layer were used to make the unit of positive electrode layers, and the paste for the negative electrode active material layer and the paste for the negative electrode current collector layer became used to make the unit from negative electrode layers. Further, the film for the solid electrolyte layer, the positive electrode layer unit, and the negative electrode layer unit were used to produce the layered body using the same method as in Example 22.

Production of the sintered body

After debinding of the obtained laminate, sintering was carried out simultaneously to obtain the sintered body. Debinding was carried out by heating to the sintering temperature of 700 ° C at a rate of 50 ° C / h in nitrogen, and holding this temperature for 10 hours. The simultaneous sintering was carried out by heating to the sintering temperature of 850 ° C at a rate of 200 ° C / h in nitrogen, and holding this temperature for 1 hour, and then it was naturally cooled after the sintering. The apparent size of the battery after simultaneous sintering was 3.2 mm * 2.5 mm * 0.4 mm.

Evaluation of the charging / discharging properties

As for the laminate obtained, the loading / unloading capacity was determined using a loading / unloading tester which was installed in a clamp which was fastened by means of pins with springs. As determination conditions, a determination was carried out with a charge / discharge current of 2 µA and a voltage of 0V ~ 1.8V. The discharge capacity determined is shown in Table 4. The threshold value of sufficient discharge properties when used was 2.5 µAh.

Example 28

Preparation of positive electrode active material and negative electrode active material

In this example, raw materials for the paste for the positive electrode active material layer and the paste for the positive electrode current collector layer were weighed out such that Li / V of lithium vanadium phosphate was 2.30. Furthermore, raw materials for the paste for the negative electrode active material layer and the paste for the negative electrode current collector layer were weighed in such a way that Li / V of lithium vanadium phosphate was 1.80. For these materials, a lithium vanadium phosphate powder was made using the same procedure as in Example 22. As for the composition of the lithium vanadium phosphate, it was confirmed by ICP that Li / V was 2.30 and 1.80. Further, with respect to the amount of bivalent V contained in V, it was confirmed by XPS that the amount of bivalent V in the lithium vanadium phosphate was 78% and 33%.

Preparation of the paste for the positive electrode active material layer and the paste for the negative electrode active material layer

Lithium vanadium phosphate powder with Li / V of 2.30 and lithium vanadium phosphate powder with Li / V of 1.80 were used to use the paste for the positive electrode active material layer and the paste for the negative electrode active material layer the same procedure as in Example 22.

Production of the paste for the solid electrolyte layer

As for the lithium aluminum titanium phosphate used as the solid electrolyte, it was weighed in such a way that f = 0.5, g = 1.0, h = 1.0, i = 2.8 j = 10.75 in the composition of Li _f Al _g Ti _h P _i O _j . Li ₂ CO ₃ , Al ₂ O ₃ , TiO ₂ and NH ₄ H ₂ PO _{4 were} used as starting materials, ethanol was used as the solvent, and wet mixing was carried out by means of a ball mill for 16 hours. After the powder mixture of the starting materials had been separated and dried from the spheres and ethanol, calcination was carried out in a crucible made of aluminum oxide at 850 ° C. in the atmosphere for 2 hours. Thereafter, the calcined powder was treated for 16 hours in ethanol using the ball mill (120 rpm / zirconium dioxide balls) for the purpose of grinding. The crushed powder was separated from the balls and ethanol and dried to obtain the powder.

Production of the solid electrolyte foil

The lithium aluminum titanium phosphate powder obtained was used to produce the solid electrolyte sheet using the same procedure as in Example 22.

Production of the paste for the positive electrode current collector layer and the paste for the negative electrode current collector layer

To make the paste for the positive electrode current collector layer and the paste for the negative electrode current collector layer, lithium vanadium phosphate powder with Li / V of 2.30, lithium vanadium phosphate powder with Li / V of 1.80 and Cu Powder using the same procedure used in Example 22.

Production of the unit from active layer material and production of the laminate

Using the same procedure as in Example 22, the paste for the positive electrode active material layer and the paste for the positive electrode current collector layer were used to make the unit of positive electrode layers, and the paste for the negative electrode active material layer and the paste for the negative electrode current collector layer became used to make the unit from negative electrode layers. Further, the film for the solid electrolyte layer, the positive electrode layer unit, and the negative electrode layer unit were used to produce the layered body using the same method as in Example 22.

Production of the sintered body

After debinding of the obtained laminate, sintering was carried out simultaneously to obtain the sintered body. Debinding was carried out by heating to the sintering temperature of 700 ° C at a rate of 50 ° C / h in nitrogen, and holding this temperature for 10 hours. The simultaneous sintering was carried out by heating to the sintering temperature of 850 ° C at a rate of 200 ° C / h in nitrogen, and holding this temperature for 1 hour, and then it was naturally cooled after the sintering. The apparent size of the battery after simultaneous sintering was 3.2 mm * 2.5 mm * 0.4 mm.

Evaluation of the charging / discharging properties

As for the laminate obtained, the loading / unloading capacity was determined using a loading / unloading tester which was installed in a clamp which was fastened by means of pins with springs. As determination conditions, a determination was carried out with a charge / discharge current of 2 µA and a voltage of 0V ~ 1.8V. The discharge capacity determined is shown in Table 4. The threshold value of sufficient discharge properties when used was 2.5 µAh.

Example 29

Preparation of positive electrode active material and negative electrode active material

In this example, raw materials for the paste for the positive electrode active material layer and the paste for the positive electrode current collector layer were weighed out such that Li / V of lithium vanadium phosphate was 2.30. Furthermore, raw materials for the paste for the negative electrode active material layer and the paste for the negative electrode current collector layer were weighed in such a way that Li / V of lithium vanadium phosphate was 1.80. For these materials, a lithium vanadium phosphate powder was made using the same procedure as in Example 22. As for the composition of the lithium vanadium phosphate, it was confirmed by ICP that Li / V was 2.30 and 1.80. Further, with respect to the amount of bivalent V contained in V, it was confirmed by XPS that the amount of bivalent V in the lithium vanadium phosphate was 78% and 33%.

Preparation of the paste for the positive electrode active material layer and the paste for the negative electrode active material layer

Lithium vanadium phosphate powder with Li / V of 2.30 and lithium vanadium phosphate powder with Li / V of 1.80 were used to use the paste for the positive electrode active material layer and the paste for the negative electrode active material layer the same procedure as in Example 22.

Production of the paste for the solid electrolyte layer

As for the lithium aluminum titanium phosphate used as the solid electrolyte, it was weighed in such a way that f = 0.5, g = 1.0, h = 2.0, i = 3.2, j = 13.75 in the composition of Li _f Al _g Ti _h P _i O _j . Li ₂ CO ₃ , Al ₂ O ₃ , TiO ₂ and NH ₄ H ₂ PO _{4 were} used as starting materials, ethanol was used as the solvent, and wet mixing was carried out by means of a ball mill for 16 hours. After the powder mixture of the starting materials had been separated and dried from the spheres and ethanol, calcination was carried out in a crucible made of aluminum oxide at 850 ° C. in the atmosphere for 2 hours. Thereafter, the calcined powder was treated for 16 hours in ethanol using the ball mill (120 rpm / zirconium dioxide balls) for the purpose of grinding. The crushed powder was separated from the balls and ethanol and dried to obtain the powder.

Production of the solid electrolyte foil

The lithium aluminum titanium phosphate powder obtained was used to produce the sheet for the solid electrolyte sheet using the same procedure as in Example 22.

Production of the paste for the positive electrode current collector layer and the paste for the negative electrode current collector layer

To prepare the paste for the positive electrode current collector layer and the paste for the negative electrode current collector layer, lithium vanadium phosphate powder with Li / V of 2.30, lithium vanadium phosphate powder with Li / V of 1.80 and Cu were used Powder using the same procedure used in Example 22.

Production of the paste for the layer unit from active material and production of the layer body

Using the same procedure as in Example 22, the paste for the positive electrode active material layer and the paste for the positive electrode current collector layer were used to make the unit of positive electrode layers, and the paste for the negative electrode active material layer and the paste for the negative electrode current collector layer became used to make the unit from negative electrode layers. Further, the film for the solid electrolyte layer, the positive electrode layer unit, and the negative electrode layer unit were used to produce the layered body using the same method as in Example 22.

Production of the sintered body

After debinding of the obtained laminate, sintering was carried out simultaneously to obtain the sintered body. The debinding was carried out by heating to the sintering temperature of 700 ° C at a rate of 50 ° C / h in nitrogen, and maintaining this temperature for 10 hours. The simultaneous sintering was carried out by heating to the sintering temperature of 850 ° C at a rate of 200 ° C / h in nitrogen, and holding this temperature for 1 hour, and then it was naturally cooled after the sintering. The apparent size of the battery after simultaneous sintering was 3.2 mm * 2.5 mm * 0.4 mm.

Evaluation of the charging / discharging properties

As for the laminate obtained, the loading / unloading capacity was determined using a loading / unloading tester which was installed in a clamp which was fastened by means of pins with springs. As determination conditions, a determination was carried out with a charge / discharge current of 2 µA and a voltage of 0V ~ 1.8V. The discharge capacity determined is shown in Table 1. The threshold value of sufficient discharge properties when used was 2.5 µAh.

Example 30

Preparation of positive electrode active material and negative electrode active material

In this example, raw materials for the paste for the positive electrode active material layer and the paste for the positive electrode current collector layer were weighed out such that Li / V of lithium vanadium phosphate was 2.30. Furthermore, raw materials for the paste for the negative electrode active material layer and the paste for the negative electrode current collector layer were weighed in such a way that Li / V of lithium vanadium phosphate was 1.80. For these materials, a lithium vanadium phosphate powder was made using the same procedure as in Example 22. As for the composition of the lithium vanadium phosphate, it was confirmed by ICP that Li / V was 2.30 and 1.80. Further, with respect to the amount of bivalent V contained in V, it was confirmed by XPS that the amount of bivalent V in the lithium vanadium phosphate was 78% and 33%.

Preparation of the paste for the positive electrode active material layer and the paste for the negative electrode active material layer

Lithium vanadium phosphate powder with Li / V of 2.30 and lithium vanadium phosphate powder with Li / V of 1.80 were used to use the paste for the positive electrode active material layer and the paste for the negative electrode active material layer the same procedure as in Example 22.

Production of the paste for the solid electrolyte layer

As for the lithium aluminum titanium phosphate used as the solid electrolyte, it was weighed in such a way that f = 3.0, g = 0.1, h = 1.0, i = 2.8, j = 10.65 in the composition of Li _f Al _g Ti _h P _i O _j . Li ₂ CO ₃ , Al ₂ O ₃ , TiO ₂ and NH ₄ H ₂ PO _{4 were} used as starting materials, ethanol was used as the solvent, and wet mixing was carried out by means of a ball mill for 16 hours. After the powder mixture of the starting materials had been separated and dried from the spheres and ethanol, calcination was carried out in a crucible made of aluminum oxide at 850 ° C. in the atmosphere for 2 hours. Thereafter, the calcined powder was treated for 16 hours in ethanol using the ball mill (120 rpm / zirconium dioxide balls) for the purpose of grinding. The crushed powder was separated from the balls and ethanol and dried to obtain the powder.

Production of the solid electrolyte foil

The lithium aluminum titanium phosphate powder obtained was used to produce the solid electrolyte sheet using the same procedure as in Example 22.

Production of the paste for the positive electrode current collector layer and the paste for the negative electrode current collector layer

To prepare the paste for the positive electrode current collector layer and the paste for the negative electrode current collector layer, lithium vanadium phosphate powder with Li / V of 2.30, lithium vanadium phosphate powder with Li / V of 1.80 and Cu were used Powder using the same procedure used in Example 22.

Production of the unit from active layer material and production of the laminate

Using the same procedure as in Example 22, the paste for the positive electrode active material layer and the paste for the positive electrode current collector layer were used to make the unit of positive electrode layers, and the paste for the negative electrode active material layer and the paste for the negative electrode current collector layer became used to make the unit from negative electrode layers. Further, the film for the solid electrolyte layer, the positive electrode layer unit, and the negative electrode layer unit were used to produce the layered body using the same method as in Example 22.

Production of the sintered body

After debinding of the obtained laminate, sintering was carried out simultaneously to obtain the sintered body. The debinding was carried out by heating to the sintering temperature of 700 ° C at a rate of 50 ° C / h in nitrogen, and maintaining this temperature for 10 hours. The simultaneous sintering was carried out by heating to the sintering temperature of 850 ° C at a rate of 200 ° C / h in nitrogen, and holding this temperature for 1 hour, and then it was naturally cooled after the sintering. The apparent size of the battery after simultaneous sintering was 3.2 mm * 2.5 mm * 0.4 mm.

Evaluation of the charging / discharging properties

As for the laminate obtained, the loading / unloading capacity was determined by means of a loading / unloading tester which was installed in the clamp, which was fastened by means of pins with springs. As determination conditions, a determination was carried out with a charge / discharge current of 2 µA and a voltage of 0V ~ 1.8V. The discharge capacity determined is shown in Table 4. The threshold value of sufficient discharge properties when used was 2.5 µAh.

Example 31

Preparation of positive electrode active material and negative electrode active material

In this example, raw materials for the paste for the positive electrode active material layer and the paste for the positive electrode current collector layer were weighed out such that Li / V of lithium vanadium phosphate was 2.30. Furthermore, for the paste for the negative electrode active material layer and the paste for the negative electrode current collector layer raw materials weighed in such a way that Li / V of lithium vanadium phosphate was 1.80. For these materials, a lithium vanadium phosphate powder was made using the same procedure as in Example 22. As for the composition of the lithium vanadium phosphate, it was confirmed by ICP that Li / V was 2.30 and 1.80. Further, with respect to the amount of bivalent V contained in V, it was confirmed by XPS that the amount of bivalent V in the lithium vanadium phosphate was 78% and 33%.

Preparation of the paste for the positive electrode active material layer and the paste for the negative electrode active material layer

Lithium vanadium phosphate powder with Li / V of 2.30 and lithium vanadium phosphate powder with Li / V of 1.80 were used to use the paste for the positive electrode active material layer and the paste for the negative electrode active material layer the same procedure as in Example 22.

Production of the paste for the solid electrolyte layer

As for the lithium aluminum titanium phosphate used as the solid electrolyte, it was weighed in such a way that f = 3.0, g = 0.1, h = 2.0, i = 3.2, j = 13.65 in the composition of Li _f Al _g Ti _h P _i O _j . Li ₂ CO ₃ , Al ₂ O ₃ , TiO ₂ and NH ₄ H ₂ PO _{4 were} used as starting materials, ethanol was used as the solvent, and wet mixing was carried out by means of a ball mill for 16 hours. After the powder mixture of the starting materials had been separated and dried from the spheres and ethanol, calcination was carried out in a crucible made of aluminum oxide at 850 ° C. in the atmosphere for 2 hours. Thereafter, the calcined powder was treated for 16 hours in ethanol using the ball mill (120 rpm / zirconia balls) for the purpose of grinding. The crushed powder was separated from the balls and the ethanol and dried to obtain the powder.

Production of the solid electrolyte foil

The lithium aluminum titanium phosphate powder obtained was used to produce the solid electrolyte sheet using the same procedure as in Example 22.

Production of the paste for the positive electrode current collector layer and the paste for the negative electrode current collector layer

To prepare the paste for the positive electrode current collector layer and the paste for the negative electrode current collector layer, lithium vanadium phosphate powder with Li / V of 2.30, lithium vanadium phosphate powder with Li / V of 1.80 and Cu Powder using the same procedure used in Example 22.

Fabrication of Unit of Active Layer Material and Fabrication of Laminate Using the same procedure as in Example 22, the paste for the positive electrode active material layer and the paste for the positive electrode current collector layer were used to make the unit of positive electrode layers, and the paste for the negative electrode active material layer and the paste for the negative electrode current collector layer were used to make the negative electrode layer unit. Further, the film for the solid electrolyte layer, the positive electrode layer unit, and the negative electrode layer unit were used to produce the layered body using the same method as in Example 22.

Production of the sintered body

After debinding of the obtained laminate, sintering was carried out simultaneously to obtain the sintered body. The debinding was carried out by heating to the sintering temperature of 700 ° C at a rate of 50 ° C / h in nitrogen, and maintaining this temperature for 10 hours. The simultaneous sintering was carried out by heating to the sintering temperature of 850 ° C at a rate of 200 ° C / h in nitrogen, and holding this temperature for 1 hour, and then it was naturally cooled after the sintering. The apparent size of the battery after simultaneous sintering was 3.2 mm * 2.5 mm * 0.4 mm.

Evaluation of the charging / discharging properties

As for the laminate obtained, the loading / unloading capacity was determined by means of a loading / unloading tester which was installed in the clamp, which was fastened by means of pins with springs. As determination conditions, a determination was carried out with a charge / discharge current of 2 µA and a voltage of 0V ~ 1.8V. The discharge capacity determined is shown in Table 4. The threshold value of sufficient discharge properties when used was 2.5 µAh.

Example 32

Preparation of positive electrode active material and negative electrode active material

In this example, raw materials for the paste for the positive electrode active material layer and the paste for the positive electrode current collector layer were weighed out such that Li / V of lithium vanadium phosphate was 2.30. Furthermore, raw materials for the paste for the negative electrode active material layer and the paste for the negative electrode current collector layer were weighed in such a way that Li / V of lithium vanadium phosphate was 1.80. For these materials, a lithium vanadium phosphate powder was made using the same procedure as in Example 22. As for the composition of the lithium vanadium phosphate, it was confirmed by ICP that Li / V was 2.30 and 1.80. Further, with respect to the amount of bivalent V contained in V, it was confirmed by XPS that the amount of bivalent V in the lithium vanadium phosphate was 78% and 33%.

Preparation of the paste for the positive electrode active material layer and the paste for the negative electrode active material layer

Lithium vanadium phosphate powder with Li / V of 2.30 and lithium vanadium phosphate powder with Li / V of 1.80 were used to use the paste for the positive electrode active material layer and the paste for the negative electrode active material layer the same procedure as in Example 22.

Production of the paste for the solid electrolyte layer

As for the lithium aluminum titanium phosphate used as the solid electrolyte, it was weighed in such a manner that f = 3.0, g = 1.0, h = 1.0, i = 2.8, j = 12.0 in the composition of Li _f Al _g Ti _h P _i O _j . Li ₂ CO ₃ , Al ₂ O ₃ , TiO ₂ and NH ₄ H ₂ PO _{4 were} used as starting materials, ethanol was used as the solvent, and wet mixing was carried out by means of a ball mill for 16 hours. After the powder mixture of the starting materials had been separated and dried from the spheres and ethanol, calcination was carried out in a crucible made of aluminum oxide at 850 ° C. in the atmosphere for 2 hours. Thereafter, the calcined powder was treated for 16 hours in ethanol using the ball mill (120 rpm / zirconium dioxide balls) for the purpose of grinding. The crushed powder was separated from the balls and ethanol and dried to obtain the powder.

Production of the solid electrolyte foil

The lithium aluminum titanium phosphate powder obtained was used to produce the solid electrolyte sheet using the same procedure as in Example 22.

Production of the paste for the positive electrode current collector layer and the paste for the negative electrode current collector layer

To prepare the paste for the positive electrode current collector layer and the paste for the negative electrode current collector layer, lithium vanadium phosphate powder with Li / V of 2.30, lithium vanadium phosphate powder with Li / V of 1.80 and Cu were used Powder using the same procedure used in Example 22.

Fabrication of Active Layer Material Unit and Laminated Body Using the same procedure as in Example 22, the paste for the positive electrode active material layer and the paste for the positive electrode current collector layer were used to make the unit of positive electrode layers, and the paste for the negative electrode active material layer and the paste for the negative electrode current collector layer were used to make the unit of negative To produce electrode layers. Further, the film for the solid electrolyte layer, the positive electrode layer unit, and the negative electrode layer unit were used to produce the layered body using the same method as in Example 22.

Production of the sintered body

After debinding of the obtained laminate, sintering was carried out simultaneously to obtain the sintered body. The debinding was carried out by heating to the sintering temperature of 700 ° C at a rate of 50 ° C / h in nitrogen, and maintaining this temperature for 10 hours. The simultaneous sintering was done by heating to the sintering temperature of 850 ° C at a rate of 200 ° C / h in nitrogen, and holding this temperature for 1 hour, and then it was naturally cooled after the sintering. The apparent size of the battery after simultaneous sintering was 3.2 mm * 2.5 mm * 0.4 mm.

Evaluation of the charging / discharging properties

As for the laminate obtained, the loading / unloading capacity was determined by means of a loading / unloading tester which was installed in the clamp, which was fastened by means of pins with springs. As determination conditions, a determination was carried out with a charge / discharge current of 2 µA and a voltage of 0V ~ 1.8V. The discharge capacity determined is shown in Table 4. The threshold value of sufficient discharge properties when used was 2.5 µAh.

Example 33

Preparation of positive electrode active material and negative electrode active material

In this example, raw materials for the paste for the positive electrode active material layer and the paste for the positive electrode current collector layer were weighed out such that Li / V of lithium vanadium phosphate was 2.30. Furthermore, raw materials for the paste for the negative electrode active material layer and the paste for the negative electrode current collector layer were weighed in such a way that Li / V of lithium vanadium phosphate was 1.80. For these materials, a lithium vanadium phosphate powder was made using the same procedure as in Example 22. As for the composition of the lithium vanadium phosphate, it was confirmed by ICP that Li / V was 2.30 and 1.80. Further, with respect to the amount of bivalent V contained in V, it was confirmed by XPS that the amount of bivalent V in the lithium vanadium phosphate was 78% and 33%.

Preparation of the paste for the positive electrode active material layer and the paste for the negative electrode active material layer

To prepare the paste for the positive electrode active material layer and the paste for the negative electrode active material layer, lithium vanadium phosphate powder with Li / V of 2.30 and lithium vanadium phosphate powder with Li / V were used using the same method as used in Example 22.

Production of the paste for the solid electrolyte layer

As for the lithium aluminum titanium phosphate used as the solid electrolyte, it was weighed in such a manner that f = 3.0, g = 1.0, h = 2.0, i = 3.2, j = 15.0 in the composition of Li _f Al _g Ti _h P _i O _j . Li ₂ CO ₃ , Al ₂ O ₃ , TiO ₂ and NH ₄ H ₂ PO _{4 were} used as starting materials, ethanol was used as the solvent, and wet mixing was carried out by means of a ball mill for 16 hours. After the powder mixture of the starting materials had been separated and dried from the spheres and ethanol, calcination was carried out in a crucible made of aluminum oxide at 850 ° C. in the atmosphere for 2 hours. Thereafter, the calcined powder was treated for 16 hours in ethanol using the ball mill (120 rpm / zirconia balls) for the purpose of grinding. The crushed powder was separated from the balls and ethanol and dried to obtain the powder.

Production of the solid electrolyte foil

The lithium aluminum titanium phosphate powder obtained was used to produce the solid electrolyte sheet using the same procedure as in Example 22.

Production of the paste for the positive electrode current collector layer and the paste for the negative electrode current collector layer

To produce the paste for the positive electrode current collector layer and the paste for the negative electrode current collector layer, lithium vanadium phosphate powder with Li / V of 2.30, lithium vanadium phosphate powder with Li / V of 1.80 and Cu were used Powder using the same procedure used in Example 22.

Fabrication of Unit of Active Layer Material and Fabrication of Laminate Using the same procedure as in Example 22, the paste for the positive electrode active material layer and the paste for the positive electrode current collector layer were used to make the unit of positive electrode layers, and the paste for the negative electrode active material layer and the paste for the negative electrode current collector layer were used to make the negative electrode layer unit. Further, the film for the solid electrolyte layer, the positive electrode layer unit, and the negative electrode layer unit were used to produce the layered body using the same method as in Example 22.

Production of the sintered body

After debinding of the obtained laminate, sintering was carried out simultaneously to obtain the sintered body. The debinding was carried out by heating to the sintering temperature of 700 ° C at a rate of 50 ° C / h in nitrogen, and maintaining this temperature for 10 hours. The simultaneous sintering was carried out by heating to the sintering temperature of 850 ° C at a rate of 200 ° C / h in nitrogen, and holding this temperature for 1 hour, and then it was naturally cooled after the sintering. The apparent size of the battery after simultaneous sintering was 3.2 mm * 2.5 mm * 0.4 mm.

Evaluation of the charging / discharging properties

As for the laminate obtained, the loading / unloading capacity was determined by means of a loading / unloading tester which was installed in the clamp, which was fastened by means of pins with springs. As determination conditions, a determination was carried out with a charge / discharge current of 2 µA and a voltage of 0V ~ 1.8V. The discharge capacity determined is shown in Table 4. The threshold value of sufficient discharge properties when used was 2.5 µAh.

Comparative Example 14

Preparation of positive electrode active material and negative electrode active material

In this comparative example, raw materials for the paste for the positive electrode active material layer and the paste for the positive electrode current collector layer were weighed in such that Li / V of lithium vanadium phosphate was 2.60. Furthermore, for the paste for the negative electrode active material layer and the paste for the negative electrode current collector layer, raw materials were weighed in such a way that Li / V of lithium vanadium phosphate was 1.48. For these materials, a lithium vanadium phosphate powder was made using the same procedure as in Example 22. As for the composition of the lithium vanadium phosphate, ICP confirmed that Li / V was 2.60 and 1.48. Further, with respect to the amount of bivalent V contained in V, it was confirmed by XPS that the amount of bivalent V in the lithium vanadium phosphate was 85% and 1%.

Preparation of the paste for the positive electrode active material layer and the paste for the negative electrode active material layer

Lithium vanadium phosphate powder with Li / V of 2.60 and lithium vanadium phosphate powder with Li / V of 1.48 were used to form the paste for the positive electrode active material layer and the paste for the layer negative electrode active material layer Using the same procedure as in Example 22.

Production of the paste for the solid electrolyte layer

As for the lithium aluminum titanium phosphate used as the solid electrolyte, it was weighed in such a way that f = 1.02, g = 0.13, h = 1.91, i = 3.0, j = 12.03 in the composition of Li _f Al _g Ti _h P _i O _j . Li ₂ CO ₃ , Al ₂ O ₃ , TiO ₂ and NH ₄ H ₂ PO _{4 were} used as starting materials, ethanol was used as the solvent, and wet mixing was carried out by means of a ball mill for 16 hours. After the powder mixture of the starting materials had been separated and dried from the spheres and ethanol, calcination was carried out in a crucible made of aluminum oxide at 850 ° C. in the atmosphere for 2 hours. Thereafter, the calcined powder was treated for 16 hours in ethanol using the ball mill (120 rpm / zirconia balls) for the purpose of grinding. The crushed powder was separated from the balls and ethanol and dried to obtain the powder.

Production of the solid electrolyte foil

The lithium aluminum titanium phosphate powder obtained was used to produce the solid electrolyte sheet using the same procedure as in Example 22.

Preparation of the paste for the positive electrode current collector layer and the paste for the negative electrode current collector layer

To prepare the paste for the positive electrode current collector layer and the paste for the negative electrode current collector layer, lithium vanadium phosphate powder with Li / V of 2.60, lithium vanadium phosphate powder with Li / V of 1.48 and Cu Powder using the same procedure used in Example 22.

Fabrication of Unit of Active Layer Material and Fabrication of Laminate Using the same procedure as in Example 22, the paste for the positive electrode active material layer and the paste for the positive electrode current collector layer were used to make the unit of positive electrode layers, and the paste for the negative electrode active material layer and the paste for the negative electrode current collector layer were used to make the negative electrode layer unit. Further, the film for the solid electrolyte layer, the positive electrode layer unit, and the negative electrode layer unit were used to produce the layered body using the same method as in Example 22.

Production of the sintered body

After debinding of the obtained laminate, sintering was carried out simultaneously to obtain the sintered body. The debinding was carried out by heating to the sintering temperature of 700 ° C at a rate of 50 ° C / h in nitrogen, and maintaining this temperature for 10 hours. The simultaneous sintering was carried out by heating to the sintering temperature of 850 ° C at a rate of 200 ° C / h in nitrogen, and holding this temperature for 1 hour, and then it was naturally cooled after the sintering. The apparent size of the battery after simultaneous sintering was 3.2 mm * 2.5 mm * 0.4 mm.

Evaluation of the charging / discharging properties

As for the laminate obtained, the loading / unloading capacity was determined by means of a loading / unloading tester which was installed in the clamp, which was fastened by means of pins with springs. As determination conditions, a determination was carried out with a charge / discharge current of 2 µA and a voltage of 0V ~ 1.8V. The discharge capacity determined is shown in Table 4. The threshold value of sufficient discharge properties when used was 2.5 µAh.

Comparative Example 15

Preparation of positive electrode active material and negative electrode active material

In this comparative example, for the paste for the positive electrode active material layer and the paste for the positive electrode current collector layer, raw materials were weighed in such a way that that Li / V of lithium vanadium phosphate was 2.60. Furthermore, for the paste for the negative electrode active material layer and the paste for the negative electrode current collector layer, raw materials were weighed in such a way that Li / V of lithium vanadium phosphate was 1.48. For these materials, a lithium vanadium phosphate powder was made using the same procedure as in Example 22. As for the composition of the lithium vanadium phosphate, ICP confirmed that Li / V was 2.60 and 1.48. Further, with respect to the amount of bivalent V contained in V, it was confirmed by XPS that the amount of bivalent V in the lithium vanadium phosphate was 85% and 1%.

Preparation of the paste for the positive electrode active material layer and the paste for the negative electrode active material layer

Lithium vanadium phosphate powder with Li / V of 2.60 and lithium vanadium phosphate powder with Li / V of 1.48 were used to use the paste for the positive electrode active material layer and the paste for the negative electrode active material layer the same procedure as in Example 22.

Production of the paste for the solid electrolyte layer

As for the lithium aluminum titanium phosphate used as the solid electrolyte, it was weighed in such a way that f = 1.5, g = 0.5, h = 1.5, i = 3.0, j = 12.0 in the composition of Li _f Al _g Ti _h P _i O _j . Li ₂ CO ₃ , Al ₂ O ₃ , TiO ₂ and NH ₄ H ₂ PO _{4 were} used as starting materials, ethanol was used as the solvent, and wet mixing was carried out by means of a ball mill for 16 hours. After the powder mixture of the starting materials had been separated and dried from the spheres and ethanol, calcination was carried out in a crucible made of aluminum oxide at 850 ° C. in the atmosphere for 2 hours. Thereafter, the calcined powder was treated for 16 hours in ethanol using the ball mill (120 rpm / zirconium dioxide balls) for the purpose of grinding. The crushed powder was separated from the balls and ethanol and dried to obtain the powder.

Production of the solid electrolyte foil

The lithium aluminum titanium phosphate powder obtained was used to produce the solid electrolyte sheet using the same procedure as in Example 22.

Production of the paste for the positive electrode current collector layer and the paste for the negative electrode current collector layer

Lithium vanadium phosphate powder with Li / V of 2.60, lithium vanadium phosphate powder with Li / V of 1.48 and Cu were used to produce the paste for the positive electrode current collector layer and the paste for the negative electrode current collector layer Powder using the same procedure used in Example 22.

Production of the unit from active layer material and production of the laminate

Using the same procedure as in Example 22, the paste for the positive electrode active material layer and the paste for the positive electrode current collector layer were used to make the unit of positive electrode layers, and the paste for the negative electrode active material layer and the paste for the negative electrode current collector layer became used to make the unit from negative electrode layers. Further, the film for the solid electrolyte layer, the positive electrode layer unit, and the negative electrode layer unit were used to produce the layered body using the same method as in Example 22.

Production of the sintered body

After debinding of the obtained laminate, sintering was carried out simultaneously to obtain the sintered body. The debinding was carried out by heating to the sintering temperature of 700 ° C at a rate of 50 ° C / h in nitrogen, and maintaining this temperature for 10 hours. The simultaneous sintering was carried out by heating to the sintering temperature of 850 ° C at a rate of 200 ° C / h in nitrogen, and holding this temperature for 1 hour, and then it was naturally cooled after the sintering. The apparent size of the battery after simultaneous sintering was 3.2 mm * 2.5 mm * 0.4 mm.

Evaluation of the charging / discharging properties

As for the laminate obtained, the loading / unloading capacity was determined by means of a loading / unloading tester which was installed in the clamp, which was fastened by means of pins with springs. As determination conditions, a determination was carried out with a charge / discharge current of 2 µA and a voltage of 0V ~ 1.8V. The discharge capacity determined is shown in Table 1. The threshold value of sufficient discharge properties when used was 2.5 µAh.

Comparative Example 16

Production of positive electrode active material and negative electrode active material

In this comparative example, raw materials for the paste for the positive electrode active material layer and the paste for the positive electrode current collector layer are weighed in such a way that Li / V of lithium vanadium phosphate was 2.60. Furthermore, for the paste for the negative electrode active material layer and the paste for the negative electrode current collector layer, raw materials were weighed in such a way that Li / V of lithium vanadium phosphate was 1.48. For these materials, a lithium vanadium phosphate powder was made using the same procedure as in Example 22. As for the composition of the lithium vanadium phosphate, ICP confirmed that Li / V was 2.60 and 1.48. Further, with respect to the amount of bivalent V contained in V, it was confirmed by XPS that the amount of bivalent V in the lithium vanadium phosphate was 85% and 1%.

Preparation of the paste for the positive electrode active material layer and the paste for the negative electrode active material layer

Lithium vanadium phosphate powder with Li / V of 2.60 and lithium vanadium phosphate powder with Li / V of 1.48 were used to use the paste for the positive electrode active material layer and the paste for the negative electrode active material layer the same procedure as in Example 22.

Production of the paste for the solid electrolyte layer

As for the lithium aluminum titanium phosphate used as the solid electrolyte, it was weighed in such a manner that f = 2.0, g = 1.0, h = 1.0, i = 3.0, j = 12.0 in the composition of Li _f Al _g Ti _h P _i O _j . Li ₂ CO ₃ , Al ₂ O ₃ , TiO ₂ and NH ₄ H ₂ PO _{4 were} used as starting materials, ethanol was used as the solvent, and wet mixing was carried out by means of a ball mill for 16 hours. After the powder mixture of the starting materials had been separated and dried from the spheres and ethanol, calcination was carried out in a crucible made of aluminum oxide at 850 ° C. in the atmosphere for 2 hours. Thereafter, the calcined powder was treated for 16 hours in ethanol using the ball mill (120 rpm / zirconium dioxide balls) for the purpose of grinding. The crushed powder was separated from the balls and ethanol and dried to obtain the powder.

Production of the solid electrolyte foil

The lithium aluminum titanium phosphate powder obtained was used to produce the solid electrolyte sheet using the same procedure as in Example 22.

Production of the paste for the positive electrode current collector layer and the paste for the negative electrode current collector layer

Lithium vanadium phosphate powder with Li / V of 2.60, lithium vanadium phosphate powder with Li / V of 1.48 and Cu were used to produce the paste for the positive electrode current collector layer and the paste for the negative electrode current collector layer Powder using the same procedure used in Example 22.

Fabrication of Active Layer Material Unit and Laminated Body Using the same procedure as in Example 22, the paste for the positive electrode active material layer and the paste for the positive electrode current collector layer were used to make the unit of positive electrode layers, and the paste for the negative electrode active material layer and the paste for the negative electrode current collector layer were used to make the unit of negative To produce electrode layers. Further, the film for the solid electrolyte layer, the positive electrode layer unit, and the negative electrode layer unit were used to produce the layered body using the same method as in Example 22.

Production of the sintered body

After debinding of the obtained laminate, sintering was carried out simultaneously to obtain the sintered body. Debinding was carried out by heating to the sintering temperature of 700 ° C at a rate of 50 ° C / h in nitrogen, and holding this temperature for 10 hours. The simultaneous sintering was carried out by heating to the sintering temperature of 850 ° C at a rate of 200 ° C / h in nitrogen, and holding this temperature for 1 hour, and then it was naturally cooled after the sintering. The apparent size of the battery after simultaneous sintering was 3.2 mm * 2.5 mm * 0.4 mm.

Evaluation of the charging / discharging properties

As for the laminate obtained, the loading / unloading capacity was determined by means of a loading / unloading tester which was installed in the clamp, which was fastened by means of pins with springs. As determination conditions, a determination was carried out with a charge / discharge current of 2 µA and a voltage of 0V ~ 1.8V. The discharge capacity determined is shown in Table 1. The threshold value of sufficient discharge properties when used was 2.5 µAh.

Comparative Example 17

Production of positive electrode active material and negative electrode active material

In this comparative example, raw materials for the paste for the positive electrode active material layer and the paste for the positive electrode current collector layer are weighed in such a way that Li / V of lithium vanadium phosphate was 2.60. Furthermore, for the paste for the negative electrode active material layer and the paste for the negative electrode current collector layer, raw materials were weighed in such a way that Li / V of lithium vanadium phosphate was 1.48. For these materials, a lithium vanadium phosphate powder was made using the same procedure as in Example 22. As for the composition of the lithium vanadium phosphate, ICP confirmed that Li / V was 2.60 and 1.48. Further, with respect to the amount of bivalent V contained in V, it was confirmed by XPS that the amount of bivalent V in the lithium vanadium phosphate was 85% and 1%.

Preparation of the paste for the positive electrode active material layer and the paste for the negative electrode active material layer

Lithium vanadium phosphate powder with Li / V of 2.60 and lithium vanadium phosphate powder with Li / V of 1.48 were used to use the paste for the positive electrode active material layer and the paste for the negative electrode active material layer the same procedure as in Example 22.

Production of the paste for the solid electrolyte layer

As for the lithium aluminum titanium phosphate used as the solid electrolyte, it was weighed in such a way that f = 0.5, g = 0.02, h = 1.0, i = 2.8, j = 9.28 in the composition of Li _f Al _g Ti _h P _i O _j . Li ₂ CO ₃ , Al ₂ O ₃ , TiO ₂ and NH ₄ H ₂ PO _{4 were} used as starting materials, ethanol was used as the solvent, and wet mixing was carried out by means of a ball mill for 16 hours. After the powder mixture of the starting materials had been separated and dried from the spheres and ethanol, calcination was carried out in a crucible made of aluminum oxide at 850 ° C. in the atmosphere for 2 hours. Thereafter, the calcined powder was treated for 16 hours in ethanol using the ball mill (120 rpm / zirconium dioxide balls) for the purpose of grinding. The crushed powder was separated from the balls and ethanol and dried to obtain the powder.

Production of the solid electrolyte foil

The lithium aluminum titanium phosphate powder obtained was used to produce the solid electrolyte sheet using the same procedure as in Example 22.

Preparation of the paste for the positive electrode current collector layer and the paste for the negative electrode current collector layer

To prepare the paste for the positive electrode current collector layer and the paste for the negative electrode current collector layer, lithium vanadium phosphate powder with Li / V of 2.60, lithium vanadium phosphate powder with Li / V of 1.48 and Cu Powder using the same procedure used in Example 22.

Fabrication of Unit of Active Layer Material and Fabrication of Laminate Using the same procedure as in Example 22, the paste for the positive electrode active material layer and the paste for the positive electrode current collector layer were used to make the unit of positive electrode layers, and the paste for the negative electrode active material layer and the paste for the negative electrode current collector layer were used to make the negative electrode layer unit. Further, the film for the solid electrolyte layer, the positive electrode layer unit, and the negative electrode layer unit were used to produce the layered body using the same method as in Example 22.

Production of the sintered body

After debinding of the obtained laminate, sintering was carried out simultaneously to obtain the sintered body. Debinding was carried out by heating to the sintering temperature of 700 ° C at a rate of 50 ° C / h in nitrogen, and holding this temperature for 10 hours. The simultaneous sintering was carried out by heating to the sintering temperature of 850 ° C at a rate of 200 ° C / h in nitrogen, and holding this temperature for 1 hour, and then it was naturally cooled after the sintering. The apparent size of the battery after simultaneous sintering was 3.2 mm * 2.5 mm * 0.4 mm.

Evaluation of the charging / discharging properties

As for the laminate obtained, the loading / unloading capacity was determined by means of a loading / unloading tester which was installed in the clamp, which was fastened by means of pins with springs. As determination conditions, a determination was carried out with a charge / discharge current of 2 µA and a voltage of 0V ~ 1.8V. The discharge capacity determined is shown in Table 1. The threshold value of sufficient discharge properties when used was 2.5 µAh.

Comparative Example 18

Preparation of positive electrode active material and negative electrode active material

In this comparative example, raw materials for the paste for the positive electrode active material layer and the paste for the positive electrode current collector layer were weighed in such that Li / V of lithium vanadium phosphate was 2.60. Further, regarding the paste for the negative electrode active material layer and the paste for the negative electrode current collector layer, raw materials were weighed in such a way that Li / V of lithium vanadium phosphate was 1.48. For these materials, a lithium vanadium phosphate powder was made using the same procedure as in Example 22. As for the composition of the lithium vanadium phosphate, ICP confirmed that Li / V was 2.60 and 1.48. Further, with respect to the amount of bivalent V contained in V, it was confirmed by XPS that the amount of bivalent V in the lithium vanadium phosphate was 85% and 1%.

Preparation of the paste for the positive electrode active material layer and the paste for the negative electrode active material layer

Lithium vanadium phosphate powder with Li / V of 2.60 and lithium vanadium phosphate powder with Li / V of 1.48 were used to use the paste for the positive electrode active material layer and the paste for the negative electrode active material layer the same procedure as in Example 22.

Production of the paste for the solid electrolyte layer

As for the lithium aluminum titanium phosphate used as the solid electrolyte, it was weighed in such a way that f = 0.5, g = 1.0, h = 2.0, i = 3.2, j = 13.75 in the composition of Li _f Al _g Ti _h P _i O _j . Li ₂ CO ₃ , Al ₂ O ₃ , TiO ₂ and NH ₄ H ₂ PO _{4 were} used as starting materials, ethanol was used as the solvent, and wet mixing was carried out by means of a ball mill for 16 hours. After the powder mixture of the starting materials had been separated and dried from the spheres and ethanol, calcination was carried out in a crucible made of aluminum oxide at 850 ° C. in the atmosphere for 2 hours. Thereafter, the calcined powder was treated for 16 hours in ethanol using the ball mill (120 rpm / zirconium dioxide balls) for the purpose of grinding. The crushed powder was separated from the balls and ethanol and dried to obtain the powder.

Production of the solid electrolyte foil

The lithium aluminum titanium phosphate powder obtained was used to produce the solid electrolyte sheet using the same procedure as in Example 22.

Production of the paste for the positive electrode current collector layer and the paste for the negative electrode current collector layer

To prepare the paste for the positive electrode current collector layer and the paste for the negative electrode current collector layer, lithium vanadium phosphate powder with Li / V of 2.60, lithium vanadium phosphate powder with Li / V of 1.48 and Cu Powder using the same procedure used in Example 22.

Production of the unit from active layer material and production of the laminate

Using the same procedure as in Example 22, the paste for the positive electrode active material layer and the paste for the positive electrode current collector layer were used to make the unit of positive electrode layers, and the paste for the negative electrode active material layer and the paste for the negative electrode current collector layer became used to make the unit from negative electrode layers. Further, the film for the solid electrolyte layer, the positive electrode layer unit, and the negative electrode layer unit were used to produce the layered body using the same method as in Example 22.

Production of the sintered body

After debinding of the obtained laminate, sintering was carried out simultaneously to obtain the sintered body. Debinding was carried out by heating to the sintering temperature of 700 ° C at a rate of 50 ° C / h in nitrogen, and holding this temperature for 10 hours. The simultaneous sintering was carried out by heating to the sintering temperature of 850 ° C at a rate of 200 ° C / h in nitrogen, and holding this temperature for 1 hour, and then it was naturally cooled after the sintering. The apparent size of the battery after simultaneous sintering was 3.2 mm * 2.5 mm * 0.4 mm.

Evaluation of the charging / discharging properties

As for the laminate obtained, the loading / unloading capacity was determined by means of a loading / unloading tester which was installed in the clamp, which was fastened by means of pins with springs. As determination conditions, a determination was carried out with a charge / discharge current of 2 µA and a voltage of 0V ~ 1.8V. The discharge capacity determined is shown in Table 4. The threshold value of sufficient discharge properties when used was 2.5 µAh.

Comparative Example 19

Preparation of positive electrode active material and negative electrode active material

In this comparative example, raw materials for the paste for the positive electrode active material layer and the paste for the positive electrode current collector layer were weighed in such that Li / V of lithium vanadium phosphate was 2.60.

Furthermore, for the paste for the negative electrode active material layer and the paste for the negative electrode current collector layer, raw materials were weighed in such a way that Li / V of lithium vanadium phosphate was 1.48. For these materials, a lithium vanadium phosphate powder was made using the same procedure as in Example 22. As for the composition of the lithium vanadium phosphate, ICP confirmed that Li / V was 2.60 and 1.48. Further, with respect to the amount of bivalent V contained in V, it was confirmed by XPS that the amount of bivalent V in the lithium vanadium phosphate was 85% and 1%.

Preparation of the paste for the positive electrode active material layer and the paste for the negative electrode active material layer

Lithium vanadium phosphate powder with Li / V of 2.60 and lithium vanadium phosphate powder with Li / V of 1.48 were used to use the paste for the positive electrode active material layer and the paste for the negative electrode active material layer the same procedure as in Example 22.

Production of the paste for the solid electrolyte layer

As for the lithium aluminum titanium phosphate used as the solid electrolyte, it was weighed in such a way that f = 3.0, g = 0.1, h = 1.0, i = 2.8, j = 10.65 in the composition of Li _f Al _g Ti _h P _i O _j . Li ₂ CO ₃ , Al ₂ O ₃ , TiO ₂ and NH ₄ H ₂ PO _{4 were} used as starting materials, ethanol was used as the solvent, and wet mixing was carried out by means of a ball mill for 16 hours. After the powder mixture of the starting materials had been separated and dried from the spheres and ethanol, calcination was carried out in a crucible made of aluminum oxide at 850 ° C. in the atmosphere for 2 hours. Thereafter, the calcined powder was treated for 16 hours in ethanol using the ball mill (120 rpm / zirconium dioxide balls) for the purpose of grinding. The crushed powder was separated from the balls and ethanol and dried to obtain the powder.

Production of the solid electrolyte foil

The lithium aluminum titanium phosphate powder obtained was used to produce the solid electrolyte sheet using the same procedure as in Example 22.

Preparation of the paste for the positive electrode current collector layer and the paste for the negative electrode current collector layer

To prepare the paste for the positive electrode current collector layer and the paste for the negative electrode current collector layer, lithium vanadium phosphate powder with Li / V of 2.60, lithium vanadium phosphate powder with Li / V of 1.48 and Cu Powder using the same procedure used in Example 22.

Fabrication of Unit of Active Layer Material and Fabrication of Laminate Using the same procedure as in Example 22, the paste for the positive electrode active material layer and the paste for the positive electrode current collector layer were used to make the unit of positive electrode layers, and the paste for the negative electrode active material layer and the paste for the negative electrode current collector layer were used to make the negative electrode layer unit. Further, the film for the solid electrolyte layer, the positive electrode layer unit, and the negative electrode layer unit were used to produce the layered body using the same method as in Example 22.

Production of the sintered body

After debinding of the obtained laminate, sintering was carried out simultaneously to obtain the sintered body. Debinding was carried out by heating to the sintering temperature of 700 ° C at a rate of 50 ° C / h in nitrogen, and holding this temperature for 10 hours. The simultaneous sintering was carried out by heating to the sintering temperature of 850 ° C at a rate of 200 ° C / h in nitrogen, and holding this temperature for 1 hour, and then it was naturally cooled after the sintering. The apparent size of the battery after simultaneous sintering was 3.2 mm * 2.5 mm * 0.4 mm.

Evaluation of the charging / discharging properties

As for the laminate obtained, the loading / unloading capacity was determined by means of a loading / unloading tester which was installed in the clamp, which was fastened by means of pins with springs. As determination conditions, a determination was carried out with a charge / discharge current of 2 µA and a voltage of 0V ~ 1.8V. The discharge capacity determined is shown in Table 4. The threshold value of sufficient discharge properties when used was 2.5 µAh.

Comparative Example 20

Preparation of positive electrode active material and negative electrode active material

In this comparative example, raw materials for the paste for the positive electrode active material layer and the paste for the positive electrode current collector layer were weighed in such that Li / V of lithium vanadium phosphate was 2.60. Further, regarding the paste for the negative electrode active material layer and the paste for the negative electrode current collector layer, raw materials were weighed in such a way that Li / V of lithium vanadium phosphate was 1.48. For these materials, a lithium vanadium phosphate powder was made using the same procedure as in Example 22. As for the composition of the lithium vanadium phosphate, ICP confirmed that Li / V was 2.60 and 1.48. Further, with respect to the amount of bivalent V contained in V, it was confirmed by XPS that the amount of bivalent V in the lithium vanadium phosphate was 85% and 1%.

Preparation of the paste for the positive electrode active material layer and the paste for the negative electrode active material layer

To prepare the paste for the positive electrode active material layer and the paste for the negative electrode active material layer, lithium vanadium phosphate powder with Li / V of 2.60 and lithium vanadium phosphate powder with Li / V of 1.48 were used using the same procedure as used in Example 22.

Production of the paste for the solid electrolyte layer

As for the lithium aluminum titanium phosphate used as the solid electrolyte, it was weighed in such a way that f = 3.0, g = 10, h = 2.0, i = 3.2, j = 15.0 in the composition of Li _f Al _g Ti _h P _i O _j . Li ₂ CO ₃ , Al ₂ O ₃ , TiO ₂ and NH ₄ H ₂ PO _{4 were} used as starting materials, ethanol was used as the solvent, and wet mixing was carried out by means of a ball mill for 16 hours. After the powder mixture of the starting materials had been separated and dried from the spheres and ethanol, calcination was carried out in a crucible made of aluminum oxide at 850 ° C. in the atmosphere for 2 hours. Thereafter, the calcined powder was treated for 16 hours in ethanol using the ball mill (120 rpm / zirconium dioxide balls) for the purpose of grinding. The crushed powder was separated from the balls and ethanol and dried to obtain the powder.

Production of the solid electrolyte foil

The lithium aluminum titanium phosphate powder obtained was used to produce the solid electrolyte sheet using the same procedure as in Example 22.

Production of the paste for the positive electrode current collector layer and the paste for the negative electrode current collector layer

To prepare the paste for the positive electrode current collector layer and the paste for the negative electrode current collector layer, lithium vanadium phosphate powder with Li / V of 2.60, lithium vanadium phosphate powder with Li / V of 1.48 and Cu Powder using the same procedure used in Example 22.

Production of the unit from active layer material and production of the laminate

Using the same procedure as in Example 22, the paste for the positive The electrode active material layer and the paste for the positive electrode current collector layer were used to make the unit from positive electrode layers, and the paste for the negative electrode active material layer and the paste for the negative electrode current collector layer were used to produce the unit from negative electrode layers. Further, the film for the solid electrolyte layer, the positive electrode layer unit, and the negative electrode layer unit were used to produce the layered body using the same method as in Example 22.

Production of the sintered body

After debinding of the obtained laminate, sintering was carried out simultaneously to obtain the sintered body. The debinding was carried out by heating to the sintering temperature of 700 ° C at a rate of 50 ° C / h in nitrogen, and maintaining this temperature for 10 hours. The simultaneous sintering was carried out by heating to the sintering temperature of 850 ° C at a rate of 200 ° C / h in nitrogen, and holding this temperature for 1 hour, and then it was naturally cooled after the sintering. The apparent size of the battery after simultaneous sintering was 3.2 mm * 2.5 mm * 0.4 mm.

Evaluation of the charging / discharging properties

As for the laminate obtained, the loading / unloading capacity was determined by means of a loading / unloading tester which was installed in the clamp, which was fastened by means of pins with springs. As determination conditions, a determination was carried out with a charge / discharge current of 2 µA and a voltage of 0V ~ 1.8V. The discharge capacity determined is shown in Table 4. The threshold value of sufficient discharge properties when used was 2.5 µAh.

It can be seen from Table 4 that the all-solid-state battery, in which lithium aluminum titanium phosphate is used as the solid-state electrolyte, can achieve a noticeably high discharge capacity in the situation in which the lithium vanadium Phosphate with Li / V and bivalent V in the range given in the present embodiment is used for the positive electrode active material layer and the negative electrode active material layer, respectively. Table 4 Positive electrode: Li / V Positive electrode: proportion of bivalent V (%) Negative electrode: Li / V Negative electrode: proportion of bivalent V (%) Li _f Al _g Ti _h P _i O _j Discharge capacity of the manufactured battery (µAh) f G H i j Example 22 2.30 78 1.80 33 1.02 0.13 1.91 3.00 12.03 5.16 Example 23 2.30 78 1.80 33 1.50 0.50 1.50 3.00 12,00 3.95 Example 24 2.30 78 1.80 33 2.00 1.00 1.00 3.00 12,00 2.65 Example 25 2.30 78 1.80 33 2.10 1.10 0.90 3.00 12,00 2.54 Example 26 2.30 78 1.80 33 0.50 0.02 1.00 2.80 9.28 3.10 Example 27 2.30 78 1.80 33 0.50 0.02 2.00 3.20 12.28 3.36 Example 28 2.30 78 1.80 33 0.50 1.00 1.00 2.80 10.75 2.89 Example 29 2.30 78 1.80 33 0.50 1.00 2.00 3.20 13.75 2.61 Example 30 2.30 78 1.80 33 3.00 0.10 1.00 2.80 10.65 2.93 Example 31 2.30 78 1.80 33 3.00 0.10 2.00 3.20 13.65 2.61 Example 32 2.30 78 1.80 33 3.00 1.00 1.00 2.80 12,00 2.80 Example 33 2.30 78 1.80 33 3.00 1.00 2.00 3.20 15.00 2.64 Comparative Example 14 2.60 85 1.48 1 1.02 0.13 1.91 3.00 12.03 1.13 Comparative Example 15 2.60 85 1.48 1 1.50 0.50 1.50 3.00 12,00 0.86 Comparative Example 16 2.60 85 1.48 1 2.00 1.00 1.00 3.00 12,00 0.41 Comparative Example 17 2.60 85 1.48 1 0.50 0.02 1.00 2.80 9.40 0.77 Comparative Example 18 2.60 85 1.48 1 0.50 1.00 2.00 3.20 13.75 0.65 Comparative Example 19 2.60 85 1.48 1 3.00 0.10 1.00 2.80 10.65 0.73 Comparative Example 20 2.60 85 1.48 1 3.00 1.00 2.00 3.20 15.00 0.66

Industrial applicability

As described above, the all-solid-state battery provided by the present invention has an effect of improving the discharge capacity.

The all-solid-state battery, which is able to provide a high capacity, makes a great contribution in the field of electronics.

LIST OF REFERENCE NUMBERS

1

All-solid-state battery

2

positive electrode layer

3

negative electrode layer

4

Solid electrolyte layer

5

packing layer

6

positive electrode current collector layer

7

positive electrode active material layer

8th

negative electrode active material layer

9

negative electrode current collector layer

QUOTES INCLUDE IN THE DESCRIPTION

This list of documents listed by the applicant has been generated automatically and is only included for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Patent literature cited

• JP 2007258165 [0006]

Claims (6)

All-solid-state battery, characterized in that the all-solid-state battery is provided between a pair of electrode layers with a solid electrolyte layer, a positive electrode active material layer forming the pair of electrode layers, and negative electrode active material layer containing lithium vanadium phosphate , the lithium vanadium phosphate contains a Li and V-containing polyphosphate compound, and meets 1.50 <Li / V≤2.30, and the proportion of bivalent V contained in V is 5% ~ 80% , All solid state battery after Claim 1 , characterized in that the solid electrolyte layer contains lithium aluminum titanium phosphate. All solid state battery after Claim 1 or 2 , characterized in that the value of Li / V of the lithium vanadium phosphate contained in the positive electrode active material layer is larger than the value of Li / V of the lithium vanadium phosphate contained in the negative electrode active material layer. All solid state battery according to one of the Claims 1 to 3 , characterized in that the lithium vanadium phosphate contained in the positive electrode active material layer satisfies 1.60≤Li / V≤2.30, and the proportion of bivalent V in V is 10% ~ 80%; and the lithium vanadium phosphate contained in the negative electrode active material layer satisfies 1.50 <Li / V≤2.10, and the proportion of bivalent V in V is 5% ~ 57%. All solid state battery according to one of the Claims 1 to 4 , characterized in that the solid electrolyte contains Li _f Al _g Ti _h P _i O _j , where f, g, h, i and j each 0.5≤f≤3.0; 0.0 <g≤1,0; 1.0 <h≤2,0;2,8≤i≤3,2; and 9.25 <j≤15.0. All solid state battery according to one of the Claims 1 to 5 , characterized in that the relative density of the pair of electrode layers and the solid electrolyte layer disposed between the pair of electrode layers is 80% or more.

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